Chromium-Catalyzed Production of Diols From Olefins

ABSTRACT

Processes for converting an olefin reactant into a diol compound are disclosed, and these processes include the steps of contacting the olefin reactant and a supported chromium catalyst comprising chromium in a hexavalent oxidation state to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst, and hydrolyzing the reduced chromium catalyst to form a reaction product comprising the diol compound. While being contacted, the olefin reactant and the supported chromium catalyst can be irradiated with a light beam at a wavelength in the UV-visible spectrum. Optionally, these processes can further comprise a step of calcining at least a portion of the reduced chromium catalyst to regenerate the supported chromium catalyst.

REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Patent Application No. 62/900,687, filed on Sep. 16, 2019, the disclosure of which is incorporated herein by reference in its entirety.

FIELD OF THE INVENTION

The present disclosure generally relates to methods for converting olefins into diols, and more particularly, relates to performing such methods with a supported chromium catalyst.

BACKGROUND OF THE INVENTION

Various diol compounds can be prepared by numerous synthesis techniques, such as the hydrolysis of epoxides, the oxidation of olefins using with acidic potassium permanganate or osmium tetroxide, and the condensation of ketones with formaldehyde followed by hydrogenation. Alternative reaction schemes are desirable. Accordingly, it is to this end that the present invention is generally directed.

SUMMARY OF THE INVENTION

This summary is provided to introduce a selection of concepts in a simplified form that are further described below in the detailed description. This summary is not intended to identify required or essential features of the claimed subject matter. Nor is this summary intended to be used to limit the scope of the claimed subject matter.

Aspects of this invention are directed to processes for converting an olefin reactant into a diol compound. For example, in one aspect, a first process can comprise (i) contacting the olefin reactant and a supported chromium catalyst comprising chromium in a hexavalent oxidation state to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst, and (ii) hydrolyzing the reduced chromium catalyst to form a reaction product comprising the diol compound. In another aspect, a second process for converting an olefin reactant into a diol compound can comprise (i) irradiating the olefin reactant and a supported chromium catalyst comprising chromium in a hexavalent oxidation state with a light beam at a wavelength in the UV-visible spectrum to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst, and (ii) hydrolyzing the reduced chromium catalyst to form a reaction product comprising the diol compound. Optionally, these processes can further comprise a step of (iii) calcining the reduced chromium catalyst to regenerate the supported chromium catalyst.

In step (i), at least a portion of the chromium on the reduced chromium catalyst can have at least one bonding site with a hydrocarboxy group (a —O-hydrocarbon group), which upon hydrolysis in step (ii), can release a diol compound analog of the olefin compound. For instance, if the olefin reactant is 1-hexene, then the diol compound can be 1,2-hexanediol.

Both the foregoing summary and the following detailed description provide examples and are explanatory only. Accordingly, the foregoing summary and the following detailed description should not be considered to be restrictive. Further, features or variations may be provided in addition to those set forth herein. For example, certain aspects may be directed to various feature combinations and sub-combinations described in the detailed description.

Definitions

To define more clearly the terms used herein, the following definitions are provided. Unless otherwise indicated, the following definitions are applicable to this disclosure. If a term is used in this disclosure but is not specifically defined herein, the definition from the IUPAC Compendium of Chemical Terminology, 2^(nd) Ed (1997), can be applied, as long as that definition does not conflict with any other disclosure or definition applied herein, or render indefinite or non-enabled any claim to which that definition is applied. To the extent that any definition or usage provided by any document incorporated herein by reference conflicts with the definition or usage provided herein, the definition or usage provided herein controls.

Herein, features of the subject matter are described such that, within particular aspects, a combination of different features can be envisioned. For each and every aspect and each and every feature disclosed herein, all combinations that do not detrimentally affect the catalysts, compositions, processes, or methods described herein are contemplated with or without explicit description of the particular combination. Additionally, unless explicitly recited otherwise, any aspect or feature disclosed herein can be combined to describe inventive catalysts, compositions, processes, or methods consistent with the present disclosure.

Generally, groups of elements are indicated using the numbering scheme indicated in the version of the periodic table of elements published in Chemical and Engineering News, 63(5), 27, 1985. In some instances, a group of elements can be indicated using a common name assigned to the group; for example, alkali metals for Group 1 elements, alkaline earth metals for Group 2 elements, transition metals for Group 3-12 elements, and halogens or halides for Group 17 elements.

The term “hydrocarbon” whenever used in this specification and claims refers to a compound containing only carbon and hydrogen, whether saturated or unsaturated. Other identifiers can be utilized to indicate the presence of particular groups in the hydrocarbon (e.g., halogenated hydrocarbon indicates the presence of one or more halogen atoms replacing an equivalent number of hydrogen atoms in the hydrocarbon). Non-limiting examples of hydrocarbons include alkanes (linear, branched, and cyclic), alkenes (olefins), and aromatics, among other compounds. Herein, cyclics and aromatics encompass fused ring compounds such as bicyclics and polycyclics.

For any particular compound or group disclosed herein, any name or structure (general or specific) presented is intended to encompass all conformational isomers, regioisomers, stereoisomers, and mixtures thereof that can arise from a particular set of substituents, unless otherwise specified. The name or structure (general or specific) also encompasses all enantiomers, diastereomers, and other optical isomers (if there are any) whether in enantiomeric or racemic forms, as well as mixtures of stereoisomers, as would be recognized by a skilled artisan, unless otherwise specified. For instance, a general reference to pentane includes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane; and a general reference to a butyl group includes a n-butyl group, a sec-butyl group, an iso-butyl group, and a t-butyl group.

Unless otherwise specified, the term “substituted” when used to describe a group, for example, when referring to a substituted analog of a particular group, is intended to describe any non-hydrogen moiety that formally replaces a hydrogen in that group, and is intended to be non-limiting. Also, unless otherwise specified, a group or groups can also be referred to herein as “unsubstituted” or by equivalent terms such as “non-substituted,” which refers to the original group in which a non-hydrogen moiety does not replace a hydrogen within that group. Moreover, unless otherwise specified, “substituted” is intended to be non-limiting and include inorganic substituents or organic substituents as understood by one of ordinary skill in the art.

The terms “contacting” and “combining” are used herein to describe catalysts, compositions, processes, and methods in which the materials or components are contacted or combined together in any order, in any manner, and for any length of time, unless otherwise specified. For example, the materials or components can be blended, mixed, slurried, dissolved, reacted, treated, impregnated, compounded, or otherwise contacted or combined in some other manner or by any suitable method or technique.

“BET surface area” as used herein means the surface area as determined by the nitrogen adsorption Brunauer, Emmett, and Teller (BET) method according to ASTM D1993-91, and as described, for example, in Brunauer, S., Emmett, P. H., and Teller, E., “Adsorption of gases in multimolecular layers,” J. Am. Chem. Soc., 60, 3, pp. 309-319, the contents of which are expressly incorporated by reference herein.

In this disclosure, while catalysts, compositions, processes, and methods are described in terms of “comprising” various components or steps, the catalysts, compositions, processes, and methods also can “consist essentially of” or “consist of” the various components or steps, unless stated otherwise.

The terms “a,” “an,” and “the” are intended to include plural alternatives, e.g., at least one. For instance, the disclosure of “an olefin reactant,” “a solid oxide,” etc., is meant to encompass one, or mixtures or combinations of more than one, olefin reactant, solid oxide, etc., unless otherwise specified.

Several types of ranges are disclosed in the present invention. When a range of any type is disclosed or claimed, the intent is to disclose or claim individually each possible number that such a range could reasonably encompass, including end points of the range as well as any sub-ranges and combinations of sub-ranges encompassed therein. For example, when a chemical compound having a certain number of carbon atoms is disclosed or claimed, the intent is to disclose or claim individually every possible number that such a range could encompass, consistent with the disclosure herein. For example, the disclosure that an olefin reactant contains a C₂ to C₁₈ olefin compound, or in alternative language, an olefin compound having from 2 to 18 carbon atoms, as used herein, refers to a compound that can have 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms, as well as any range between these two numbers (for example, a C₂ to C₈ olefin compound), and also including any combination of ranges between these two numbers (for example, a C₂ to C₄ olefin compound and a C₈ to C₁₂ olefin compound).

Similarly, another representative example follows for the amount of chromium on the supported chromium catalyst consistent with aspects of this invention. By a disclosure that the amount of chromium can be in a range from about 0.1 to about 15 wt. %, the intent is to recite that the amount of chromium can be any amount in the range and, for example, can be equal to about 0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about 1, about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, about 10, about 11, about 12, about 13, about 14, or about 15 wt. %. Additionally, the amount of chromium can be within any range from about 0.1 to about 15 wt. % (for example, from about 0.1 to about 5 wt. %), and this also includes any combination of ranges between about 0.1 and about 15 wt. % (for example, the amount of chromium can be in a range from about 0.5 to about 2.5 wt. %, or from about 5 to about 15 wt. %). Further, in all instances, where “about” a particular value is disclosed, then that value itself is disclosed. Thus, the disclosure that the amount of chromium can be from about 0.1 to about 15 wt. % also discloses an amount of chromium from 0.1 to 15 wt. % (for example, from 0.1 to 5 wt. %), and this also includes any combination of ranges between 0.1 and 15 wt. % (for example, the amount of chromium can be in a range from 0.5 to 2.5 wt. %, or from 5 to 15 wt. %). Likewise, all other ranges disclosed herein should be interpreted in a manner similar to these examples.

The term “about” means that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but can be approximate including being larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement errors, and the like, and other factors known to those of skill in the art. In general, an amount, size, formulation, parameter or other quantity or characteristic is “about” or “approximate” whether or not expressly stated to be such. The term “about” also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial mixture. Whether or not modified by the term “about,” the claims include equivalents to the quantities. The term “about” can mean within 10% of the reported numerical value, and often within 5% of the reported numerical value.

Although any methods, devices, and materials similar or equivalent to those described herein can be used in the practice or testing of the invention, the typical methods, devices, and materials are herein described.

All publications and patents mentioned herein are incorporated herein by reference for the purpose of describing and disclosing, for example, the constructs and methodologies that are described in the publications, which might be used in connection with the presently described invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is generally directed to the conversion of an olefin into an analogous diol compound. Unexpectedly, it was found that the combined use of a supported chromium catalyst, light reduction, and hydrolysis can efficiently convert the olefin (e.g., a normal α-olefin) into the analogous diol, and beneficially, even at ambient temperature. Also unexpectedly, it was found that in some olefin-to-diol transformations, light reduction was not required, such as for certain normal α-olefin reactants.

Processes for Converting Olefins into Diols

Disclosed herein are processes for converting an olefin reactant into a diol compound. A first process can comprise (i) contacting the olefin reactant and a supported chromium catalyst comprising chromium in a hexavalent oxidation state to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst, and (ii) hydrolyzing the reduced chromium catalyst to form a reaction product comprising the diol compound. A second process can comprise (i) irradiating the olefin reactant and a supported chromium catalyst comprising chromium in a hexavalent oxidation state with a light beam at a wavelength in the UV-visible spectrum to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst, and (ii) hydrolyzing the reduced chromium catalyst to form a reaction product comprising the diol compound. The reduced chromium catalyst has an average oxidation state less than that of the supported chromium catalyst.

While not wishing to be bound by theory, it is believed that in step (i) of the first and second processes, at least a portion of the chromium on the reduced chromium catalyst can have at least one bonding site with a hydrocarboxy group (a —O-hydrocarbon group), which upon hydrolysis in step (ii), can release a diol compound analog of the olefin reactant. For instance, and not wishing to be bound by theory, a double alkoxide linkage may be formed with α-olefins, in which the first and second carbons bond to adjacent oxygens on the reduced chromium catalyst, which upon hydrolysis can release a 1,2-diol compound analog of the α-olefin reactant.

Generally, the features of the first process and the second process (e.g., the olefin reactant, the supported chromium catalyst, the reduced chromium catalyst, the light beam, and the conditions under which the contacting step (or the irradiating step) and the hydrolyzing step are conducted, among others) are independently described herein and these features can be combined in any combination to further describe the disclosed processes to produce diol compounds. Moreover, additional process steps can be performed before, during, and/or after any of the steps in any of the processes disclosed herein, and can be utilized without limitation and in any combination to further describe these processes, unless stated otherwise. Further, any diol compounds produced in accordance with the disclosed processes are within the scope of this disclosure and are encompassed herein.

A variety of olefin reactants can be used in the processes to form a diol compound, inclusive of linear olefin compounds (e.g., normal α-olefins), branched olefin compounds, cyclic olefin compounds, and the like, as well as combinations thereof. Any suitable carbon number olefin can be used, such that the olefin reactant can comprise a Cn olefin compound (and the diol compound often can comprise a Cn diol compound). While not being limited thereto, the integer n can range from 2 to 36 in one aspect, from 2 to 18 in another aspect, from 2 to 12 in yet another aspect, and from 2 to 8 in still another aspect.

Therefore, the olefin reactant can comprise any suitable carbon number olefin compound, for instance, a C₂ to C₃₆ olefin compound; alternatively, a C₂ to C₁₈ olefin compound; alternatively, a C₂ to C₁₂ olefin compound; alternatively, a C₂ to C₈ olefin compound; alternatively, a C₂-C₁₅ normal α-olefin compound; or alternatively, a C₂-C₈ normal α-olefin compound. If desired, the olefin reactant can contain a single olefin compound of relatively high purity, such as at least about 90 wt. % of a single olefin compound, at least about 95 wt. % of a single olefin compound, at least about 98 wt. % of a single olefin compound, or at least about 99 wt. % of a single olefin compound, and so forth. Alternatively, the olefin reactant can comprise a mixture of two or more olefin reactants, such as two or more olefin compounds in any relative proportions. Thus, the olefin reactant can comprise a mixture of C₂ to C₃₆ olefin compounds, a mixture of C₂ to C₁₈ olefin compounds, a mixture of C₂ to C₁₂ olefin compounds, or a mixture of C₂ to C₈ olefin compounds, and the like.

Illustrative examples of olefin reactants can include ethylene, propylene, butene, pentene, hexene, heptene, octene, decene, dodecene, tetradecene, hexadecene, octadecene, and the like, as well as combinations thereof. In a non-limiting aspect, the olefin reactant can comprise ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-octadecene, styrene, and the like, as well as combinations thereof. In another aspect, the olefin reactant can comprise ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and the like, or any combination thereof. In yet another aspect, the olefin reactant can comprise ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and the like, or any combination thereof. In still another aspect, the olefin reactant can comprise norbornene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, and the like, or any combination thereof.

In the second process, the olefin reactant and the supported chromium catalyst can be irradiated with a light beam at a wavelength in the UV-visible spectrum, while in the first process, the olefin reactant and the supported chromium catalyst can be contacted in the absence of light irradiation. While light irradiation is beneficial and may be needed for certain olefin-to-diol transformations, it is not required for all olefin-to-diol transformations. For instance, and unexpectedly, α-olefins such as 1-pentene and 1-hexene are sufficiently reactive with the supported chromium catalyst to produce diols after hydrolysis in the absence of any light irradiation.

Generally, the contacting step of the first process can be performed under any conditions sufficient to accommodate the contacting of the olefin reactant and the supported chromium catalyst (comprising chromium in a hexavalent oxidation state) to form the reduced chromium catalyst (having a lower oxidation state), while the irradiating step of the second process can be performed under any conditions sufficient to accommodate the irradiation of the olefin reactant and the supported chromium catalyst (comprising chromium in a hexavalent oxidation state) with a light beam and to form the reduced chromium catalyst (having a lower oxidation state). For instance, the relative amount (or concentration) of the olefin reactant to the amount of chromium (in the supported chromium catalyst) can alter the efficacy of the reduction process. In certain aspects, the molar ratio of the olefin reactant to the chromium (in the supported chromium catalyst) can be at least about 0.25:1, at least about 0.5:1, at least about 1:1, at least about 10:1, at least about 100:1, at least about 1000:1, or at least about 10,000:1. Thus, a large excess of the olefin reactant can be used, and there is no particular limit as to the maximum amount of olefin reactant.

The temperature and pressure of the contacting step (or the irradiating step) can be such that the olefin reactant remains a liquid throughout reduction of the supported chromium catalyst in one aspect, and the olefin reactant remains a gas throughout reduction of the supported chromium catalyst in another aspect. Advantageously, it was found that reducing supported chromium compounds at ambient temperatures was achieved in both the first process and the second process disclosed herein. Nonetheless, in certain aspects, the contacting step (or the irradiating step) can be conducted at a temperature of less than about 200° C., less than about 100° C., less than about 70° C., less than about 40° C., from about 0° C. to about 200° C., from about −100° C. to about 100° C., from about 0° C. to about 100° C., or from about 10° C. to about 40° C., and can produce a reduced chromium catalyst (e.g., with at least a portion of the chromium on the reduced chromium catalyst having at least one bonding site with a hydrocarboxy group). These temperature ranges also are meant to encompass circumstances where the contacting (or the irradiating) is performed at a series of different temperatures, instead of at a single fixed temperature, falling within the respective temperature ranges, wherein at least one temperature is within the recited ranges.

In the first process, the contacting step can be further characterized by an amount of time that the olefin reactant and the supported chromium catalyst are contacted or combined, e.g., a contact time. The contact time must be sufficient to allow the reduction of the supported chromium catalyst to occur, whether the reduction occurs very rapidly or very slowly. Thus, in certain aspects, and not being limited thereto, the contact time can be in a range from about 15 sec to about 48 hr, from about 15 sec to about 24 hr, from about 1 hr to about 8 hr, from about 15 min to about 4 hr, from about 1 min to about 6 hr, from about 5 min to about 1 hr, from about 10 min to about 2 hr, from about 1 min to about 1 hr, or from about 1 min to about 15 min. Agitation, mixing, or other suitable technique can be used to ensure that the mixture of the supported chromium catalyst (e.g., particles) and the olefin reactant is uniformly combined.

Likewise, in the second process, the irradiating step can be further characterized by an amount of time that the olefin reactant and the supported chromium catalyst are exposed to the light beam, e.g., an exposure time. Without being bound by theory, it is believed that exposure to the light beam in the presence of the olefin reactant is responsible for the reduction of the supported chromium catalyst, and therefore it follows that the exposure time must be sufficient to allow this transformation to occur, whether the transformation occurs very rapidly or very slowly. Thus, in certain aspects, and not being limited thereto, the exposure time can be in a range from about 15 sec to about 48 hr, from about 15 sec to about 24 hr, from about 1 hr to about 8 hr, from about 15 min to about 4 hr, from about 1 min to about 6 hr, from about 5 min to about 1 hr, from about 10 min to about 2 hr, from about 1 min to about 1 hr, or from about 1 min to about 15 min. As one of skill in the art would recognize, the exposure time can vary based on the intensity of the light beam, the wavelength(s) of the light beam, and so forth. Agitation, mixing, or other suitable technique can be used to ensure that the mixture of the supported chromium catalyst (e.g., particles) and the olefin reactant is uniformly exposed to the light beam irradiation.

The supported chromium catalyst and the olefin reactant can be continuously subjected to irradiation (for the entirety of the exposure time), or the irradiation can be pulsed (such that the total of the pulses equates to the exposure time, e.g., sixty 1-sec pulses equates to a 60-sec exposure time). Combinations of periods of continuous irradiation and pulsed irradiation can be utilized, if desired.

In the second process, irradiation of a supported chromium catalyst with a light beam in the UV-visible spectrum, in the presence of an olefin reactant, results in a chromium catalyst with a reduced oxidation state (e.g., a reduced chromium catalyst). A wide range of wavelengths, light sources, and intensities can be used, as long as these wavelengths, light sources, and intensities are sufficient to reduce at least a portion of the hexavalent chromium species present in the supported chromium catalyst. In certain aspects, for instance, the light can be derived from any suitable source, such as from sunlight, a fluorescent white light, an LED diode, and/or a UV lamp. The distance from non-sunlight sources can be varied as needed (e.g., minimized) to increase the effectiveness of the irradiation.

The wavelength of the light can be any in the range of UV-visible light. In certain aspects, the wavelength of the light beam can be a single wavelength, or more than one wavelength, such as a range of wavelengths. For instance, the wavelength of the light beam can be a range of wavelengths spanning at least 25 nm, at least 50 nm, at least 100 nm, at least 200 nm, or at least 300 nm. In one aspect, the wavelength of the light beam can comprise a single wavelength or a range of wavelengths in the UV spectrum, in the visible spectrum (from 380 nm to 780 nm), or both. In another aspect, the wavelength of the light beam can comprise a single wavelength or a range of wavelengths in the 200 nm to 750 nm range. Yet, in another aspect, the wavelength of the light beam can comprise a single wavelength or a range of wavelengths in the 300 to 750 nm range, the 350 nm to 650 nm range, the 300 nm to 600 nm range, the 300 nm to 500 nm range, or the 400 nm to 500 nm range. In other aspects, the wavelength of the light beam can comprise a single wavelength or a range of wavelengths below 600 nm, below 525 nm, or below 500 nm; additionally or alternatively, above 300 nm, above 350 nm, above 400 nm, or above 450 nm.

The light beam of the irradiating step also can be characterized by its intensity (e.g., the total amount of light emitted from a source). In certain aspects, the light beam can have an intensity of at least about 500 lumens, at least about 1,000 lumens, at least about 2,000 lumens at least about 5,000 lumens, at least about 10,000 lumens, at least about 20,000 lumens, at least about 50,000 lumens, or at least about 100,000 lumens. Thus, there may not be an upper limit on the intensity of the light source. Alternatively, the light beam can have an intensity in a range from about 50 to about 50,000 lumens, from about 50 to about 10,000 lumens, from about 100 to about 5,000 lumens, or from about 500 to about 2,000 lumens. Additionally, the light beam can be characterized by the amount of light reaching the olefin reactant and supported chromium catalyst, i.e., the flux.

In certain aspects, the olefin reactant and the supported chromium catalyst comprising chromium in a hexavalent oxidation state can be irradiated by at least about 100 lux, at least about 500 lux, at least about 1000 lux, at least about 2000 lux, at least about 5000 lux, at least about 10,000 lux, at least about 20,000 lux, at least about 100,000 lux, or in a range from about 10,000 to about 1,000,000 lux, from about 50,000 to about 500,000 lux, or from about 50,000 to about 200,000 lux. Additionally or alternatively, in certain aspects, the olefin reactant and the supported chromium catalyst comprising chromium in the hexavalent oxidation state can be irradiated with a light beam having a power of at least about 50 watts, at least about 100 watts, at least about 200 watts, at least about 500 watts, at least about 1,000 watts, or at least about 2,000 watts.

Any suitable reactor or vessel can be used to form the diol compound, non-limiting examples of which can include a flow reactor, a continuous reactor, a packed bed reactor, a fluidized bed reactor, and a stirred tank reactor, including more than one reactor in series or in parallel, and including any combination of reactor types and arrangements.

In one aspect, the olefin reactant can be in a gas phase during the contacting step (or the irradiating step). In another aspect, the olefin reactant can be in a liquid phase during the contacting step (or the irradiating step). In another aspect, the disclosed processes can comprise contacting (or irradiating) a slurry (e.g., a loop slurry) of the solid supported chromium catalyst in the olefin reactant. In yet another aspect, the disclosed processes can comprise contacting the olefin reactant with a fluidized bed of the solid supported chromium catalyst (or irradiating while contacting or fluidizing the supported chromium catalyst). In still another aspect, the disclosed processes can comprise contacting the olefin reactant (e.g., in the gas phase or in the liquid phase) with a fixed bed of the solid supported chromium catalyst (or irradiating while contacting). As a skilled artisan would recognize, there are other methods for contacting/irradiating the olefin reactant and the solid supported chromium catalysts, and the disclosed processes are not limited solely to those disclosed herein. For instance, the olefin reactant and the supported chromium catalyst can be mixed or contacted in a stirred tank (or irradiated while being mixed in the stirred tank).

Any suitable pressure can be used to contact the olefin reactant and the supported catalyst and to form the reduced chromium catalyst, and such can depend upon the carbon number of the olefin reactant (and its boiling point), the type of reactor configuration and desired mode for contacting/irradiating the olefin reactant with the (solid) supported chromium catalyst, among other considerations.

Often, the process for forming the reduced chromium catalyst (and subsequently, the diol compound) can be a flow process and/or a continuous process. In such circumstances, the olefin reactant-supported chromium catalyst contact time (or reaction time) can be expressed in terms of weight hourly space velocity (WHSV) the ratio of the weight of the olefin reactant which comes in contact with a given weight of the supported chromium catalyst per unit time (units of g/g/hr, or hr⁻¹).

While not limited thereto, the WHSV employed for the disclosed processes can have a minimum value of 0.01 hr⁻¹, 0.02 hr⁻¹, 0.05 hr⁻¹, 0.1 hr⁻¹, 0.25 hr⁻¹, or 0.5 hr⁻¹; or alternatively, a maximum value of 500 hr⁻¹, 400 hr⁻¹, 300 hr⁻¹, 100 hr⁻¹, 50 hr⁻¹, 10 hr⁻¹, 5 hr⁻¹, 2 hr⁻¹, or 1 hr⁻¹. Generally, the WHSV can be in a range from any minimum WHSV disclosed herein to any maximum WHSV disclosed herein. In a non-limiting aspect, the WHSV can be in a range from about 0.01 hr⁻¹ to about 500 hr⁻¹; alternatively, from about 0.01 hr⁻¹ to about 10 hr⁻¹; alternatively, from about 0.01 hr⁻¹ to about 1 hr⁻¹; alternatively, from about 0.02 hr⁻¹ to about 400 hr⁻¹; alternatively, from about 0.02 hr⁻¹ to about 50 hr⁻¹; alternatively, from about 0.05 hr⁻¹ to about 300 hr⁻¹; alternatively, from about 0.05 hr⁻¹ to about 5 hr⁻¹; alternatively, from about 0.1 hr⁻¹ to about 400 hr⁻¹; alternatively, from about 0.25 hr⁻¹ to about 50 hr⁻¹; alternatively, from about 0.25 hr⁻¹ to about 2 hr⁻¹; alternatively, from about 0.5 hr⁻¹ to about 400 hr⁻¹; alternatively, from about 0.5 hr⁻¹ to about 5 hr⁻¹; or alternatively, from about 0.5 hr⁻¹ to about 2 hr⁻¹. Other WHSV ranges are readily apparent from this disclosure.

Referring now to the hydrolyzing step, in which the reduced chromium catalyst (e.g., with at least a portion of the chromium on the reduced chromium catalyst having at least one bonding site with a hydrocarboxy group) is hydrolyzed to form a reaction product comprising the diol compound. Generally, the temperature, pressure, and time features of the hydrolyzing step can be the same as those disclosed herein for the contacting step or irradiating step, although not limited thereto. For example, the hydrolyzing step can be conducted at a temperature of less than about 200° C., less than about 100° C., less than about 70° C., less than about 40° C., from about 0° C. to about 200° C., from about 0° C. to about 100° C., or from about 10° C. to about 40° C., and can result in the formation of a reaction product containing the diol compound. These temperature ranges also are meant to encompass circumstances where the hydrolyzing step is performed at a series of different temperatures, instead of at a single fixed temperature, falling within the respective temperature ranges, wherein at least one temperature is within the recited ranges.

While not limited thereto, the hydrolyzing step can comprise contacting the reduced chromium catalyst with a hydrolysis agent. Illustrative and non-limiting examples of suitable hydrolysis agents can include water, steam, an alcohol agent, an acid agent, an alkaline agent, and the like, as well as combinations thereof. Thus, mixtures of water and various alcohol agents, such as C₁-C₄ alcohols (and/or acid agents, such as hydrochloric acid, sulfuric acid, acetic acid, ascorbic acid, and the like; and/or alkaline agents, such as sodium hydroxide, ammonium hydroxide, and the like) in any relative proportions can be used as the hydrolysis agent. Thus, the pH of the hydrolysis agent(s) can range from acid to neutral to basic pH values, generally encompassing a pH range from about 1 (or less) to about 13-13.5.

Optionally, the hydrolysis agent can further comprise any suitable reducing agent, and representative reducing agents include ascorbic acid, iron (II) reducing agents, zinc reducing agents, and the like, as well as combinations thereof. These are sometimes useful for preventing unwanted secondary oxidations by unreacted chromium (VI). Further, they also can be used to tailor the product range by increasing selectivity. For example, in some aspects, adding reducing agents to the hydrolysis agent can eliminate all carbonyl products and instead produce only alcohol products.

As disclosed herein, the reaction product can comprise a diol compound, which can be an analog of the olefin reactant. Thus, typical diol compounds that can synthesized using the processes disclosed herein can include, for instance, ethanediol (ethylene glycol), propanediol (propylene glycol), a butanediol, a pentanediol, a hexanediol, and the like, as well as combinations thereof. Further, the diol compounds that can be synthesized using the processes disclosed herein can include a 1,2-diol compound, or a 1,3-diol compound, or a 2,3-diol compound, or any combination of a 1,2-diol compound, a 1,3-diol compound, and/or a 2,3-diol compound.

In addition to or in lieu of the diol compound, the reaction product can comprise an alcohol compound (a mono-alcohol compound) and/or a carbonyl compound, such as an aldehyde compound, a ketone compound, or a carboxylic acid compound, as well as any combination of alcohol, aldehyde, ketone, and carboxylic acid compounds. Thus, enols are encompassed herein, since the reaction product can comprise an alcohol compound, a carbonyl compound, or both.

The processes described herein result in an unexpectedly high conversion of the olefin reactant and/or yield to the diol compound. In one aspect, the minimum conversion (or yield) can be at least about 2 wt. %, at least about 5 wt. %, at least about 10 wt. %, at least about 15 wt. %, or at least about 25 wt. %. Additionally, the maximum conversion (or yield) can be about 50 wt. %, about 70 wt. % about 80 wt. %, about 90 wt. %, about 95 wt. %, or about 99 wt. %, and can approach 100% conversion of the olefin reactant (or yield of the diol compound). Generally, the conversion (or yield) can be in a range from any minimum conversion (or yield) disclosed herein to any maximum conversion (or yield) disclosed herein. Non-limiting ranges of conversion (or yield) can include from about 5 wt. % to about 99 wt. %, from about 10 wt. % to about 95 wt. %, or from about 15 wt. % to about 70 wt. %. For conversion, the percentages are the amount of the olefin reactant converted based on the initial amount of the olefin reactant. The yield values are weight percentages, and are based on the weight of the diol compound produced to the weight of olefin reactant. In some aspects, these conversions (or yields) can be achieved in a batch process, while in other aspects, these conversions (or yields) can be achieved in a flow or continuous process, such as, for example, a single pass or multiple passes through a reactor (e.g., a fixed bed reactor). Often, the conversion and yield can be manipulated by varying the ratio of reductant olefin feed to the amount of chromium (VI), and by varying other reaction conditions such as time, temperature, and irradiation.

Also unexpectedly, continuous flow processes for producing the diol compound in accordance with this invention have unexpectedly high single pass conversions of the olefin reactant (or single pass yields to the desired diol compound). In one aspect, the minimum single pass conversion (or yield) can be at least about 2 wt. %, at least about 5 wt. %, at least about 10 wt. %, at least about 15 wt. %, or at least about 25 wt. %. Additionally, the maximum single pass conversion (or yield) can be about 50 wt. %, about 70 wt. %, about 80 wt. %, about 90 wt. %, about 95 wt. %, or about 99 wt. %, and can approach 100% conversion of the olefin reactant (or yield of the diol compound), depending upon the reaction conditions. Generally, the single pass conversion (or yield) can be in a range from any minimum single pass conversion (or yield) disclosed herein to any maximum single pass conversion (or yield) disclosed herein. Non-limiting ranges of single pass conversion (or yield) can include from about 5 wt. % to about 99 wt. %, from about 10 wt. % to about 95 wt. %, or from about 15 wt. % to about 70 wt. %.

The yield of the diol compound also can be characterized based on the amount of chromium (VI) (of the supported chromium catalyst). For instance, the molar ratio (molar yield) of the diol compound based on the moles of chromium (VI) can be at least about 0.01 moles, at least about 0.02 moles, at least about 0.05 moles, at least about 0.1 moles, or at least about 0.25 moles (and up to 2 moles, up to about 1.8 moles, up to about 1.6 moles, up to about 1.4 moles, up to about 1.2 moles, or up to about 1 mole) of the diol compound per mole of chromium (VI). If more than one diol compound is produced, then this ratio represents the total moles of diol compounds produced per mole of chromium (VI) of the supported chromium catalyst.

The processes to produce the diol compounds disclosed herein typically can result in—after hydrolysis—a crude reaction mixture containing residual olefin reactant (e.g., 1-hexene), a desired diol compound (e.g., 1,2-hexanediol), and by-products. In many instances, it can be desirable to isolate or separate at least a portion (and in some cases, all) of the olefin reactant from the reaction product after step (ii). This can be accomplished using any suitable technique, which can include but is not limited to, extraction, filtration, evaporation, or distillation, as well as combinations of two or more of these techniques. In particular aspects of this invention, the isolating or separating step utilizes distillation at any suitable pressure (one or more than one distillation column can be used).

Additionally or alternatively, the processes disclosed herein can further comprise a step of separating at least a portion (and in some cases, all) of the diol compound from the reaction product, and any suitable technique can be used, such as extraction, filtration, evaporation, distillation, or any combination thereof. Additionally or alternatively, the processes disclosed herein can further comprise a step of separating at least a portion (and in some cases, all) of the reduced chromium catalyst from the reaction product after step (ii), and as above, any suitable technique(s) can be used.

Optionally, certain components of the reaction product—such as the olefin reactant—can be recovered and recycled to the reactor. In such instances, the olefin reactant can be recycled and contacted/irradiated with supported chromium catalyst again, such that the overall conversion of the olefin reactant is increased after multiple contacts with the supported chromium catalyst (or multiple passes through the reactor containing the supported chromium catalyst).

If desired, the processes disclosed herein can further comprise a step of (iii) calcining at least a portion (and in some cases, all) of the reduced chromium catalyst to regenerate the supported chromium catalyst. Any suitable calcining conditions can be used, for instance, subjecting the reduced chromium catalyst to an oxidizing atmosphere at any suitable peak temperature and time conditions, such as a peak temperature from about 300° C. to about 1000° C., from about 500° C. to about 900° C., or from about 550° C. to about 870° C., for a time period of from about 1 min to about 24 hr, from about 1 hr to about 12 hr, or from about 30 min to about 8 hr.

The calcining step can be conducted using any suitable technique and equipment, whether batch or continuous. For instance, the calcining step can be performed in a belt calciner or, alternatively, a rotary calciner. In some aspects, the calcining step can be performed in a batch or continuous calcination vessel comprising a fluidized bed. As would be recognized by those of skill in the art, other suitable techniques and equipment can be employed for the calcining step, and such techniques and equipment are encompassed herein.

An illustrative and non-limiting example of the processes disclosed herein follows for the case in which a C₂-C₈ olefin is the reactant, and a C₂-C₈ diol is the diol product. In this case, the first process for converting a C₂-C₈ olefin into a C₂-C₈ diol can comprise (i) contacting the C₂-C₈ olefin and a supported chromium catalyst comprising chromium in a hexavalent oxidation state to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst, and (ii) hydrolyzing the reduced chromium catalyst (with any suitable hydrolysis agent) to form a reaction product comprising the C₂-C₈ diol compound. The second process for converting a C₂-C₈ olefin into a C₂-C₈ diol can comprise (i) irradiating the C₂-C₈ olefin and a supported chromium catalyst comprising chromium in a hexavalent oxidation state with a light beam at a wavelength in the UV-visible spectrum to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst, and (ii) hydrolyzing the reduced chromium catalyst (with any suitable hydrolysis agent) to form a reaction product comprising the C₂-C₈ diol.

The C₂-C₈ olefin can comprise ethylene (or propylene, or 1-butene, or 1-pentene, or 1-hexene) and the C₂-C₈ diol can comprise ethanediol (or propanediol, or a butanediol, or a pentanediol, or a hexanediol). Often, the C₂-C₈ diol can comprise a 1,2-diol compound. Moreover, as discussed herein, the process to convert a C₂-C₈ olefin into a C₂-C₈ diol optionally can further comprise a step of (iii) calcining at least a portion (and in some cases, all) of the reduced chromium catalyst to regenerate the supported chromium catalyst.

Another illustrative and non-limiting example of the processes disclosed herein follows for the case in which a 1-olefin or an α-olefin is the reactant (or a 2-olefin, where the double bond is between the 2nd and 3rd carbon atoms), and a 1,2-diol is the diol compound (or a 2,3-diol is the diol compound). In this case, the first process for converting an α-olefin (or a 2-olefin) into a 1,2-diol (or a 2,3-diol) can comprise (i) contacting the α-olefin (or the 2-olefin) and a supported chromium catalyst comprising chromium in a hexavalent oxidation state to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst, and (ii) hydrolyzing the reduced chromium catalyst (with any suitable hydrolysis agent) to form a reaction product comprising the 1,2-diol compound (or the 2,3-diol compound). The second process for converting an α-olefin (or a 2-olefin) into a 1,2-diol (or a 2,3-diol) can comprise (i) irradiating the α-olefin (or the 2-olefin) and a supported chromium catalyst comprising chromium in a hexavalent oxidation state with a light beam at a wavelength in the UV-visible spectrum to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst, and (ii) hydrolyzing the reduced chromium catalyst (with any suitable hydrolysis agent) to form a reaction product comprising the 1,2-diol (or the 2,3-diol). For example, if the olefin reactant is 1-hexene, the diol compound can comprise (or consist essentially of, or consist of) 1,2-hexanediol, while if the olefin reactant is 2-hexene, the diol compound can comprise (or consist essentially of, or consist of) 2,3-hexanediol. Moreover, as discussed herein, these processes can further comprise a step of (iii) calcining at least a portion (and in some cases, all) of the reduced chromium catalyst to regenerate the supported chromium catalyst.

Chromium Catalysts

Generally, these disclosed processes are applicable to the reduction of any hexavalent chromium catalyst, and are not limited to the reduction of any particular type of supported chromium catalyst comprising chromium in a hexavalent oxidation state. Thus, supported chromium catalysts contemplated herein encompass those prepared by contacting a support with a chromium-containing compound—representative and non-limiting examples of the chromium-compound compound include chromium (III) acetate, basic chromium (III) acetate, chromium (III) acetylacetonate, Cr₂(SO₄)₃, Cr(NO₃)₃, and CrO₃—and calcining in an oxidizing atmosphere to form a supported chromium catalyst. In these aspects, chromium can be impregnated during, or prior to, the calcination step, which can be conducted at a variety of temperatures and time periods, and can be generally selected to convert all or a portion of the chromium to hexavalent chromium. The methods disclosed herein can comprise reducing at least a portion of the hexavalent chromium species to a reduced oxidation state—for instance, Cr (II) and/or Cr (III) and/or Cr (IV), and/or Cr (V) species, any of which may be present on the reduced chromium catalyst.

Any suitable chromium-containing compound (or chromium precursor) can be used as a chromium component to prepare the supported chromium catalyst. Illustrative and non-limiting examples of chromium (II) compounds can include chromium (II) acetate, chromium (II) chloride, chromium (II) bromide, chromium (II) iodide, chromium (II) sulfate, and the like, as well as combinations thereof. Likewise, illustrative and non-limiting examples of chromium (III) compounds can include a chromium (III) carboxylate, a chromium (III) naphthenate, a chromium (III) halide, chromium (III) sulfate, chromium (III) nitrate, a chromium (III) dionate, and the like, as well as combinations thereof. In some aspects, the chromium-containing compound can comprise chromium (III) acetate, chromium (III) acetylacetonate, chromium (III) chloride, chromium (III) bromide, chromium (III) sulfate, chromium (III) nitrate, and the like, as well as combinations thereof.

While not required, it can be beneficial for the chromium-containing compound to be soluble in a hydrocarbon solvent during preparation of the supported chromium catalyst. In such situations, the chromium-containing compound can comprise tertiary butyl chromate, a diarene chromium (0) compound, bis-cyclopentadienyl chromium (II), chromium (III) acetylacetonate, chromium acetate, and the like, or any combination thereof. Similarly, and not required, it can be beneficial for the chromium-containing compound to be soluble in water during preparation of the supported chromium catalyst. In such situations, the chromium-containing compound can comprise chromium trioxide, chromium acetate, chromium nitrate, and the like, or any combination thereof.

Various solid supports can be used for the supported chromium catalyst (and the reduced chromium catalyst), such as conventional solid oxides and zeolites. Generally, the solid oxide can comprise oxygen and one or more elements selected from Group 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 of the periodic table, or comprise oxygen and one or more elements selected from the lanthanide or actinide elements (See: Hawley's Condensed Chemical Dictionary, 11^(th) Ed., John Wiley & Sons, 1995; Cotton, F. A., Wilkinson, G., Murillo, C. A., and Bochmann, M., Advanced Inorganic Chemistry, 6^(th) Ed., Wiley-Interscience, 1999). For example, the solid oxide can comprise oxygen and an element, or elements, selected from Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn, and Zr. Illustrative examples of solid oxide materials or compounds that can be used as solid support can include, but are not limited to, Al₂O₃, B₂O₃, BeO, Bi₂O₃, CdO, CO₃O₄, Cr₂O₃, CuO, Fe₂O₃, Ga₂O₃, La₂O₃, Mn₂O₃, MoO₃, NiO, P₂O, Sb₂O₅, SiO₂, SnO₂, SrO, ThO₂, TiO₂, V₂O₅, WO₃, Y₂O₃, ZnO, ZrO₂, and the like, including mixed oxides thereof, and combinations thereof.

The solid oxide can encompass oxide materials such as silica, “mixed oxide” compounds thereof such as silica-titania, and combinations or mixtures of more than one solid oxide material. Mixed oxides such as silica-titania can be single or multiple chemical phases with more than one metal combined with oxygen to form the solid oxide. Examples of mixed oxides that can be used as solid oxide include, but are not limited to, silica-alumina, silica-coated alumina, silica-titania, silica-zirconia, alumina-titania, alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria, aluminum phosphate, aluminophosphate, aluminophosphate-silica, titania-zirconia, and the like, or a combination thereof. In some aspects, the solid support can comprise silica, silica-alumina, silica-coated alumina, silica-titania, silica-titania-magnesia, silica-zirconia, silica-magnesia, silica-boria, aluminophosphate-silica, and the like, or any combination thereof. Silica-coated aluminas are encompassed herein; such oxide materials are described in, for example, U.S. Pat. Nos. 7,884,163 and 9,023,959, incorporated herein by reference in their entirety.

The percentage of each oxide in a mixed oxide can vary depending upon the respective oxide materials. As an example, a silica-alumina (or silica-coated alumina) typically has an alumina content from 5 wt. % to 95 wt. %. According to one aspect, the alumina content of the silica-alumina (or silica-coated alumina) can be from 5 wt. % alumina 50 wt. % alumina, or from 8 wt. % to 30 wt. % alumina. In another aspect, high alumina content silica-aluminas (or silica-coated aluminas) can be employed, in which the alumina content of these materials typically ranges from 60 wt. % alumina to 90 wt. % alumina, or from 65 wt. % alumina to 80 wt. % alumina.

In one aspect, the solid oxide can comprise silica-alumina, silica-coated alumina, silica-titania, silica-zirconia, alumina-titania, alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria, aluminum phosphate, aluminophosphate, aluminophosphate-silica, titania-zirconia, or a combination thereof; alternatively, silica-alumina; alternatively, silica-coated alumina; alternatively, silica-titania; alternatively, silica-zirconia; alternatively, alumina-titania; alternatively, alumina-zirconia; alternatively, zinc-aluminate; alternatively, alumina-boria; alternatively, silica-boria; alternatively, aluminum phosphate; alternatively, aluminophosphate; alternatively, aluminophosphate-silica; or alternatively, titania-zirconia.

In another aspect, the solid oxide can comprise silica, alumina, titania, thoria, stania, zirconia, magnesia, boria, zinc oxide, a mixed oxide thereof, or any mixture thereof. In yet another aspect, the solid support can comprise silica, alumina, titania, or a combination thereof, alternatively, silica; alternatively, alumina; alternatively, titania; alternatively, zirconia; alternatively, magnesia; alternatively, boria; or alternatively, zinc oxide. In still another aspect, the solid oxide can comprise silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, silica-titania, silica-yttria, silica-zirconia, alumina-titania, alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria, aluminophosphate-silica, titania-zirconia, and the like, or any combination thereof.

Consistent with certain aspects of this invention, the supported chromium catalyst and the reduced chromium catalyst can comprise a chemically-treated solid oxide as the support, and where the chemically-treated solid oxide comprises a solid oxide (any solid oxide disclosed herein) treated with an electron-withdrawing anion (any electron withdrawing anion disclosed herein). The electron-withdrawing component used to treat the solid oxide can be any component that increases the Lewis or Brønsted acidity of the solid oxide upon treatment (as compared to the solid oxide that is not treated with at least one electron-withdrawing anion). According to one aspect, the electron-withdrawing component can be an electron-withdrawing anion derived from a salt, an acid, or other compound, such as a volatile organic compound, that serves as a source or precursor for that anion. Examples of electron-withdrawing anions can include, but are not limited to, sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, phospho-tungstate, tungstate, molybdate, and the like, including mixtures and combinations thereof. In addition, other ionic or non-ionic compounds that serve as sources for these electron-withdrawing anions also can be employed.

It is contemplated that the electron-withdrawing anion can be, or can comprise, fluoride, chloride, bromide, phosphate, triflate, bisulfate, or sulfate, and the like, or any combination thereof, in some aspects provided herein. In other aspects, the electron-withdrawing anion can comprise sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, and the like, or combinations thereof. Yet, in other aspects, the electron-withdrawing anion can comprise fluoride and/or sulfate.

The chemically-treated solid oxide generally can contain from about 1 wt. % to about 30 wt. % of the electron-withdrawing anion, based on the weight of the chemically-treated solid oxide. In particular aspects provided herein, the chemically-treated solid oxide can contain from about 1 to about 20 wt. %, from about 2 wt. % to about 20 wt. %, from about 3 wt. % to about 20 wt. %, from about 2 wt. % to about 15 wt. %, from about 3 wt. % to about 15 wt. %, from about 3 wt. % to about 12 wt. %, or from about 4 wt. % to about 10 wt. %, of the electron-withdrawing anion, based on the total weight of the chemically-treated solid oxide.

In an aspect, the chemically-treated solid oxide can comprise fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, fluorided-chlorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, and the like, as well as any mixture or combination thereof.

In another aspect, the chemically-treated solid oxide employed in the supported chromium catalyst and the reduced chromium catalyst and the processes described herein can be, or can comprise, a fluorided solid oxide and/or a sulfated solid oxide, non-limiting examples of which can include fluorided alumina, sulfated alumina, fluorided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, fluorided silica-coated alumina, sulfated silica-coated alumina, and the like, as well as combinations thereof. Additional information on chemically-treated solid oxide can be found in, for instance, U.S. Pat. Nos. 7,294,599, 7,601,665, 7,884,163, 8,309,485, 8,623,973, and 8,703,886, which are incorporated herein by reference in their entirety.

Representative examples of supported chromium catalysts and reduced chromium catalysts (in which a solid oxide is the support) include, but are not limited to, chromium/silica, chromium/silica-titania, chromium/silica-titania-magnesia, chromium/silica-alumina, chromium/silica-coated alumina, chromium/aluminophosphate, chromium/alumina, chromium/alumina borate, and the like, or any combination thereof. In one aspect, for instance, the supported chromium catalyst and the reduced chromium catalyst can comprise chromium/silica, while in another aspect, the supported chromium catalyst and the reduced chromium catalyst can comprise chromium/silica-titania, and in yet another aspect, the supported chromium catalyst and the reduced chromium catalyst can comprise chromium/silica-alumina and/or chromium/silica-coated alumina. In circumstances in which the supported chromium catalyst and the reduced chromium catalyst comprise chromium/silica-titania, any suitable amount of titanium can be present, including from about 0.1 to about 20 wt. %, from about 0.5 to about 15 wt. %, from about 1 to about 10 wt. %, or from about 1 to about 6 wt. % titanium, based on the total weight of the supported chromium catalyst and the reduced chromium catalyst.

Representative examples of supported chromium catalysts and reduced chromium catalysts (in which a chemically-treated solid oxide is the support) include, but are not limited to, chromium/sulfated alumina, chromium/fluorided alumina, chromium/fluorided silica-alumina, chromium/fluorided silica-coated alumina, and the like, as well as combinations thereof.

Consistent with certain aspects of this invention, the supported chromium catalyst and the reduced chromium catalyst can comprise a zeolite as the support, i.e., a chromium supported zeolite. Any suitable zeolite can be used, for instance, large pore and medium pore zeolites. Large pore zeolites often have average pore diameters in a range of from about 7 Å to about 12 Å, and non-limiting examples of large pore zeolites include L-zeolite, Y-zeolite, mordenite, omega zeolite, beta zeolite, and the like. Medium pore zeolites often have average pore diameters in a range of from about 5 Å to about 7 Å. Combinations of zeolitic supports can be used.

Additional representative examples of zeolites that can be used in the supported chromium catalyst and the reduced chromium catalyst include, for instance, a ZSM-5 zeolite, a ZSM-11 zeolite, a EU-1 zeolite, a ZSM-23 zeolite, a ZSM-57 zeolite, an ALPO4-11 zeolite, an ALPO4-41 zeolite, a Ferrierite framework type zeolite, and the like, or any combination thereof.

In the supported chromium catalyst and the reduced chromium catalyst, the zeolite can be bound with a support matrix (or binder), non-limiting examples of which can include silica, alumina, magnesia, boria, titania, zirconia, various clays, and the like, including mixed oxides thereof, as well as mixtures thereof. For example, the supported chromium catalyst and the reduced chromium catalyst support can comprise a binder comprising alumina, silica, a mixed oxide thereof, or a mixture thereof. The zeolite can be bound with the binder using any method known in the art. While not being limited thereto, the supported chromium catalyst and the reduced chromium catalyst can comprise a zeolite and from about 3 wt. % to about 35 wt. % binder; alternatively, from about 5 wt. % to about 30 wt. % binder; or alternatively, from about 10 wt. % to about 30 wt. % binder. These weight percentages are based on the total weight of the supported chromium catalyst or the reduced chromium catalyst.

The amount of chromium in the supported chromium catalyst and the reduced chromium catalyst also is not particularly limited. However, the amount of chromium in the supported chromium catalyst and the reduced chromium catalyst typically ranges from about 0.01 to about 50 wt. %; alternatively, from about 0.01 to about 20 wt. %; alternatively, from about 0.01 to about 10 wt. %; alternatively, from about 0.05 to about 15 wt. %; alternatively, from about 0.1 to about 15 wt. %; alternatively, from about 0.2 to about 10 wt. %; alternatively, from about 0.1 to about 5 wt. %; alternatively, from about 0.5 to about 30 wt. %; or alternatively, from about 0.5 to about 2.5 wt. %. These weight percentages are based on the amount of chromium relative to the total weight of the supported chromium catalyst or the reduced chromium catalyst. While not wishing to be bound by theory, it is believed that lower chromium loadings (e.g., 1 wt. % and less) can result in higher selectivity to a particular diol compound, while higher chromium loadings (e.g., 5-15 wt. % and above) can result in higher diol yields per gram of catalyst.

Likewise, the amount of chromium in an average oxidation state of +5 or less in the reduced chromium catalyst is not particularly limited, and can fall within the same ranges. Thus, the reduced chromium catalyst can contain from about 0.01 to about 50 wt. %, from about 0.01 to about 20 wt. %, from about 0.01 to about 10 wt. %, from about 0.05 to about 15 wt. %, from about 0.1 to about 15 wt. %, from about 0.2 to about 10 wt. %, from about 0.1 to about 5 wt. %, from about 0.5 to about 30 wt. %, or from about 0.5 to about 2.5 wt. % of chromium in an average oxidation state of +5 or less, based on the total weight of the reduced chromium catalyst.

Generally, at least about 10 wt. % of the chromium in the supported chromium catalyst is present in a hexavalent oxidation state before the reduction step, and more often at least about 20 wt. % is present as chromium (VI). In further aspects, at least about 40 wt. %, at least about 60 wt. %, at least about 80 wt. %, at least about 90 wt. %, or at least about 95 wt. %, of the chromium in the supported chromium catalyst can be present in an oxidation state of +6. These weight percentages are based on the total amount of chromium. Traditional chromium (VI) catalysts often will have an orange, yellow, or tan color, indicating the presence of chromium (VI).

Conversely, less than or equal to about 50 wt. % of the chromium in the reduced chromium catalyst is typically present in an oxidation state of +6 (VI), and more often less than or equal to about 40 wt. %. In further aspects, less than or equal to about 30 wt. %, or less than or equal to about 15 wt. % of chromium in the reduced chromium catalyst can be present in an oxidation state of +6. The minimum amount of chromium (VI) often can be 0 wt. % (no measurable amount), at least about 0.5 wt. %, at least about 1 wt. %, at least about 2 wt. %, or at least about 5 wt. %. These weight percentages are based on the total amount of chromium. The reduced chromium catalysts often will have a green, blue, gray, or black color.

Thus, the contacting (optionally, with irradiation) of the supported chromium catalyst with the olefin reactant ordinarily results in at least about 10 wt. %, at least about 20 wt. %, at least about 40 wt. %, at least about 60 wt. %, at least about 80 wt. %, or at least about 90 wt. %, of the supported chromium catalyst being reduced or converted to form the reduced chromium catalyst.

Additionally or alternatively, the chromium in the reduced chromium catalyst can be characterized by an average valence of less than or equal to about 5.25. More often, the chromium in the reduced chromium catalyst has an average valence of less than or equal to about 5; alternatively, an average valence of less than or equal to about 4.75; alternatively, an average valence of less than or equal to about 4.5; alternatively, an average valence of less than or equal to about 4.25; or alternatively, an average valence of less than or equal to about 4.

The total pore volume of the supported chromium catalyst and the reduced chromium catalyst is not particularly limited, and high pore volume is not required for the disclosed processes. For instance, the supported chromium catalyst and the reduced chromium catalyst can have a total pore volume in a range from about 0.1 to about 5 mL/g, from about 0.15 to about 5 mL/g, from about 0.1 to about 3 mL/g, from about 0.5 to about 2.5 mL/g, or from about 0.15 to about 2 mL/g. Likewise, the surface area of the supported chromium catalyst and the reduced chromium catalyst is not limited to any particular range. Generally, however, the supported chromium catalyst and the reduced chromium catalyst can have a BET surface area in a range from about 50 to about 2000 m²/g, from about 50 to about 700 m²/g, from about 50 to about 400 m²/g, from about 100 to about 1200 m²/g, from about 150 to about 525 m²/g, or from about 300 to about 1000 m²/g.

The supported chromium catalyst and the reduced chromium catalyst can have any suitable shape or form, and such can depend on the type of process that is employed to convert the olefin reactant into the diol compound (e.g., fixed bed versus fluidized bed). Illustrative and non-limiting shapes and forms include powder, round or spherical (e.g., a sphere), ellipsoidal, pellet, bead, cylinder, granule (e.g., regular and/or irregular), trilobe, quadrilobe, ring, wagon wheel, monolith, and the like, as well as any combination thereof. Accordingly, various methods can be utilized to prepare the supported chromium catalyst particles, including, for example, extrusion, spray drying, pelletizing, marumerizing, spherodizing, agglomeration, oil drop, and the like, as well as combinations thereof.

In some aspects, the supported chromium catalyst and the reduced chromium catalyst have a relatively small particle size, in which representative ranges for the average (d50) particle size of the supported chromium catalyst and the reduced chromium catalyst can include from about 10 to about 500 microns, from about 25 to about 250 microns, from about 20 to about 100 microns, from about 40 to about 160 microns, or from about 40 to about 120 microns.

In other aspects, the supported chromium catalyst and the reduced chromium catalyst can be in the form of pellets or beads—and the like—having an average size ranging from about 1/16 inch to about ½ inch, or from about ⅛ inch to about ¼ inch. As noted above, the size of the supported chromium catalyst and/or reduced chromium catalyst particles can be varied to suit the particular process for converting the olefin reactant into the diol.

Examples 1-67

The invention is further illustrated by the following examples, which are not to be construed in any way as imposing limitations to the scope of this invention. Various other aspects, modifications, and equivalents thereof, which after reading the description herein, can suggest themselves to one of ordinary skill in the art without departing from the spirit of the present invention or the scope of the appended claims.

Catalyst A was a Cr/silica catalyst containing 1 wt. % Cr, with a BET surface area of 500 m²/g, a pore volume of 1.6 mL/g, and an average particle size of 100 μm. Prior to use, the catalyst was calcined in air at 650° C. for 3 hr to form the chromium (VI)/silica catalyst containing 0.97 wt. % hexavalent Cr.

Catalyst B was a Cr/silica-titania catalyst containing 1 wt. % Cr and 4.2 wt. % TiO₂, with a BET surface area of 500 m²/g, a pore volume of 2.5 mL/g, and an average particle size of 130 μm. Prior to use, the catalyst was calcined in air at 850-870° C. for 3 hr to form the chromium (VI)/silica-titania catalyst containing 0.95 wt. % hexavalent Cr.

Catalyst C was a Cr/silica containing 10 wt. % Cr, the silica having a BET surface area of 500 m²/g, a pore volume of 1.6 mL/g, and an average particle size of 100 μm. Prior to use, the catalyst was calcined in air at 400° C. for 3 hr to form the chromium (VI)/silica catalyst containing 5 wt. % hexavalent Cr.

Catalyst D was a Cr/silica-titania containing 0.8 wt. % Cr and 7.5 wt. % TiO₂, with a BET surface area of 550 m²/g, a pore volume of 2.5 mL/g, and an average particle size of 130 μm. Prior to use, the catalyst was calcined in air at 850° C. for 3 hr to form the chromium (VI)/silica-titania catalyst containing 0.8 wt. % hexavalent Cr.

Catalyst E was a Cr/silica containing 0.28 wt. % Cr, with a BET surface area of 500 m²/g, a pore volume of 1.6 mL/g, and an average particle size of 100 μm. Prior to use, the catalyst was calcined in air at 750° C. for 3 hr to form the chromium (VI)/silica catalyst containing 0.28 wt. % hexavalent Cr.

Catalyst F was a Cr/silica containing 5 wt. % Cr, with a BET surface area of 500 m²/g, a pore volume of 1.6 mL/g, and an average particle size of 100 μm. Prior to use, the catalyst was calcined in air at 500° C. for 3 hr to form the chromium (VI)/silica catalyst containing 4 wt. % hexavalent Cr.

Catalysts G1-G2 were prepared by dissolving CrO₃ in water, then impregnating the resulting solution onto an alumina (boehmite) with a BET surface area of 300 m²/g and a pore volume of 1.3 mL/g to equal 5 wt. % Cr. After drying and prior to use, the catalysts were calcined in air at 500° C. (G1) or 600° C. (G2) for 3 hr to form the chromium (VI)/alumina catalysts containing 4.5 wt. % hexavalent Cr.

Catalysts H1-H2 were prepared by dissolving CrO₃ in water, then impregnating the resulting solution onto a silica-coated alumina (40 wt. % silica, BET surface area of 450 m²/g, pore volume of 1.4 mL/g, average particle size of 25 μm) to equal 5 wt. % Cr. After drying and prior to use, the catalysts were calcined in air at 500° C. (H1) or 600° C. (H2) for 3 hr to form the chromium (VI)/silica-coated alumina catalysts.

Catalyst J was prepared by dissolving K₂Cr₂O₇ in water, then impregnating the resulting solution onto a silica (BET surface area of 500 m²/g, pore volume of 1.6 mL/g, average particle size of 100 μm) to equal 5 wt. % Cr. After drying and prior to use, the catalyst was calcined in air at 500° C. for 3 hr to form the chromium (VI)/silica catalyst containing 5 wt. % hexavalent Cr.

Catalyst K was prepared by dissolving K₂Cr₂O₇ in water, then impregnating the resulting solution onto a silica (BET surface area of 500 m²/g, pore volume of 1.6 mL/g, average particle size of 100 μm) to equal 10 wt. % Cr. After removing excess water, the catalyst was heat treated in air at 100° C. for 3 hr to form the chromium (VI)/silica catalyst containing 10 wt. % hexavalent Cr.

Catalyst L was prepared by dissolving K₂Cr₂O₇ in water, then impregnating the resulting solution onto a silica (BET surface area of 500 m²/g, pore volume of 1.6 mL/g, average particle size of 100 μm) to equal 10 wt. % Cr. After removing excess water, the catalyst was heat treated in air at 200° C. for 3 hr to form the chromium (VI)/silica catalyst containing 10 wt. % hexavalent Cr.

BET surface areas can be determined using the BET nitrogen adsorption method of Brunauer et al., J. Am. Chem. Soc., 60, 309 (1938) as described in ASTM D1993-91. Total pore volumes can be determined in accordance with Halsey, G. D., J. Chem. Phys. (1948), 16, pp. 931. The d50 particle size, or median or average particle size, refers to the particle size for which 50% of the sample by volume has a smaller size and 50% of the sample has a larger size, and can be determined using laser diffraction in accordance with ISO 13320.

Table I summarizes the reactions of Examples 1-67, in which the supported chromium catalyst was first charged to an air-tight glass container at 25° C. (or a different temperature if specified), followed by the addition of the hydrocarbon reactant. The glass container was then exposed to a light source as noted in Table I. For all examples where the glass container was exposed to light, the container was slowly rotated at 5-10 rpm to turn over the catalyst particles in the bottle to ensure even exposure of the mixture of the supported chromium catalyst and the hydrocarbon reactant to each other and to the light. Samples exposed to sunlight were taken outside and placed in direct sunlight. For examples where the glass container was exposed to artificial light, the sample was placed in a box containing a fluorescent light or a LED light, where three 15 watt bulbs were placed in a plane about 3 inches apart and about 2 inches from the bottle. Reduction of the supported chromium catalysts was monitored by the presence of a color change. Each supported chromium catalyst comprising chromium in the hexavalent oxidation state had an orange color which darkened significantly upon exposing the supported chromium catalyst to light in the presence of the hydrocarbon reactant, and usually assuming a green or blue color, indicating reduction of the supported chromium catalyst starting material, and formation of the reduced chromium catalyst.

After the desired exposure time, the reduced chromium catalyst was mixed with a hydrolysis agent to cleave the hydrocarbon-containing ligand from the reduced chromium catalyst. The mixture was stirred for several minutes. The hydrolysis agent used was generally selected so as to not interfere with analysis of the reaction product (e.g., methanol was not used as the hydrolysis agent when the reaction product after hydrolysis could contain methanol, etc.).

Table I summarizes the results of Examples 1-67, and lists the specific supported chromium catalyst and amount, the hydrocarbon reactant and amount, the light treatment and resulting color, the hydrolysis agent and amount, the acid/Cr (molar), alcohol/Cr (molar), the GC-MS/Cr (molar), the total/Cr (molar), and an analysis of the reaction product (oxygenated products) after hydrolysis. The reaction product analysis includes only oxygen-containing products that were derivable from the reductant/reactant and does not include, for example, materials resulting from the hydrolysis agent or its by-products, or oligomers resulting from polymerization. For the oxygenated reaction products, area % from the analytical procedures listed below is roughly equivalent to mol %, thus the results in Table I are shown in mol %.

Carboxylic acid products (and acid/Cr ratios on a molar basis) were determined by first neutralizing the product acids with a solution of sodium hydroxide to put them into the ionic form. Then, a small amount of the sample was injected through an ion column designed to separate anions from weak organic acids through an ion chromatography process. A Dionex IC-3000 instrument with an ICE-AS1 column and guard was used. The test was specifically sensitive to linear carboxylic acids from C₁ to C₆, glutarate and glycolate ions. Results were reported in micrograms of carboxylate per mL of solution, which was then converted to moles.

Lower alcohol products (and alcohol/Cr on a molar basis) were determined using a GC-MS procedure, with an Agilent 6890 gas chromatograph having a flame-ionizing detector (FID). It used a Restek Stapilwax column (P/N 10658) designed and gated specifically to separate and detect light alcohols. The procedure was gated for acetone, methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, t-butanol, 2-butanol, 2-butoxyethanol, acetonitrile and tetrahydrofuran.

Additional reaction products (and GC-MS/Cr on a molar basis) were determined using another GC-MS procedure, as follows. Gas chromatography was performed using an Agilent 7890B GC equipped with both flame ionizing and mass spectral analysis. An all-purpose capillary column (Agilent J&W VF-5 ms, 30 m×0.25 mm×0.25 μm) was used with variable temperature. Approximate 0.5 μL sample aliquots were injected into a GC port held at 250° C. using a split ratio of 10:1. The carrier gas was ultra-high purity helium and was electronically controlled throughout the run to a constant flow rate of 1.2 mL/min. Initial column temperature was held at 50° C. for 5 min, ramped at 20° C./min to 250° C., and then held at 250° C. for 19 min. Spectral assignment was made via mass correlation using an Agilent 5977B mass spectrometer connected to the GC unit using electron ionization at 70 eV. The nominal mass range scanned was 14-400 m/z using a scan time of 0.5 sec. Nominal detector voltage used was 1200 V. For calibration purposes both the FID and MS detectors were sometimes used in sequence on the same or reference samples.

Due to the wide range of oxygenated products produced herein, one or all of these three procedures were used to characterize the reaction product after hydrolysis. In some cases, the same compound was detected by more than one technique, and this was subtracted out of the total/Cr (on a molar basis) to prevent double counting of the same compound by more than one analytical technique. For the most part, however, there was very little overlap between the three analytical procedures.

Referring now to the data in Table I, Examples 1-10 demonstrate the unexpected conversion of methane into methanol at ambient temperature using a variety of supported chromium catalysts, irradiation treatments, and hydrolysis agents. Note that Examples 1-4 used only one analytical technique and showed a product stream that was 100% methanol, whereas Examples 6-10 used all three analytical techniques and resulted in product streams containing 66-97 mol % methanol, the balance being formic acid.

Similar successful results were found for the conversion of ethane into ethanol, isobutane into t-butanol/i-butanol, n-pentane into 2-pentanol/1-pentanol, cyclopentane into cyclopentanol, n-hexane into various hexanols, cyclohexane into cyclohexanol, and toluene into benzaldehyde/benzyl alcohol. When the hydrocarbon reactant was i-pentane, the oxygenated reaction product contained a variety of alcohol and carbonyl products, whereas when the reactant was dichloromethane, no conversion to an alcohol or carbonyl was noted. While the focus of these examples was not to maximize chromium conversion (or yield to any particular alcohol or carbonyl compound), the total/Cr molar value in Table I illustrates that significant chromium conversion and alcohol/carbonyl yield can be achieved, depending of course on the reductant, the catalyst (and chromium loading), and the irradiation conditions, among other factors.

When the reactant was an olefin, it was found that the GC-MS analytical technique was necessary to identify diol products, thus examples in which this technique was not used may give an incomplete representation of the oxygenated product mix. Generally, examples that utilized ethylene as the reductant formed a reaction product (even when used at −78° C. to prevent polymerization) after hydrolysis that included ethanediol and methanol, ethanol, formic acid, and/or acetic acid. The lower reaction temperatures seemed to favor selectivity to the diol. Examples that utilized 1-pentene as the reductant formed a reaction product (even with no light irradiation, see Example 44) after hydrolysis that included a pentanediol (e.g., 1,2-pentanediol) and various acids and other alcohols (e.g., formic acid and butanol). Examples that utilized 1-hexene or 2-hexene as the reductant formed a reaction product (even with no light irradiation, see Example 55) after hydrolysis that included a hexanediol (e.g., 1,2-hexanediol and/or 2,3-hexanediol and/or 3,4-hexanediol) and various acids and other alcohols. Table I demonstrates that these olefins are very reactive and, therefore, the reaction product typically contained a mixture of mono-alcohols, diols, aldehydes, ketones, and/or carboxylic acids.

TABLE I Summary of Examples 1-67 (products in mol %) Example 1 2 3 4 Catalyst A B A B Weight (g) 2.7 2.0 1.8 2.0 Reductant Methane Methane Methane Methane Amount 10 psig 10 psig 10 psig 10 psig Light 4 hr Sun 4 hr Sun 6 hr Sun 6 hr Sun Color Green Green Green Green Hydrolysis H₂O/Ether H₂O/Ether H₂O H₂O Amount (mL) 20 20 20 20 Acid/Cr 0 0 0 Alcohol/Cr 1.013 0.272 0.261 0.173 GC-MS/Cr Total/Cr 1.013 0.272 0.261 0.173 Oxygenated methanol 100% methanol 100% methanol 100% methanol 100% Products Example 5 6 7 8 Catalyst D E J F Weight (g) 2.1 2.8 2.2 2.1 Reductant Methane Methane Methane Methane Amount 15 psig 15 psig 15 psig 15 psig Light 44 hr Blue 67 hr Blue 67 hr Blue 67 hr Blue Color Olive green Olive green Red-brown Dark brown-black Hydrolysis H₂O + CH₃CN H₂O + CH₃CN H₂O + CH₃CN H₂O + CH₃CN Amount (mL) 15 15 15 15 Acid/Cr 0.009 0.010 0.007 0.008 Alcohol/Cr 0.284 0.320 0.030 0.073 GC-MS/Cr 0.007 0.000 0 0.0025 Total/Cr 0.300 0.330 0.037 0.081 Oxygenated methanol 96% methanol 97% methanol 80% methanol 90% Products formic acid  4% formic acid  3% formic acid 20% formic acid 10% Example 9 10 11 12 Catalyst H2 G2 D B Weight (g) 2.2 2.0 2.0 2.1 Reductant Methane Methane Dichloromethane Ethane Amount 15 psig 15 psig 0.5 mL 15 psig Light 67 hr Blue 67 hr Blue 7 hr Blue 72 hr Blue Color Dark brown Dark brown Olive Green Blue-gray Hydrolysis H₂O + CH₃CN H₂O + CH₃CN 10% H₂O/MeOH H₂O Amount (mL) 15 15 40 20 Acid/Cr 0.003 0.002 0.042 Alcohol/Cr 0.025 0.004 0.366 GC-MS/Cr 0.000 0.000 0.000 0.000 Total/Cr 0.028 0.006 0.000 0.408 Oxygenated methanol 91% methanol 66% No Products ethanol 72% Products formic acid  9% formic acid 34% Detected methanol 16% formic acid  6% hexanoic acid  3% acetic acid  1% pentanoic acid  1% Example 13 14 15 16 Catalyst D D B B Weight (g) 1.9 2.5 2.6 1.9 Reductant Ethane i-Butane n-Pentane n-Pentane Amount 15 psig 10 psig 0.75 mL 0.75 mL Light 30 hr Blue 6 hr UV 1 hr UV 3.3 hr UV Color Blue-gray Green Blue-gray Blue-gray Hydrolysis H₂O + CH₃CN 4% H₂O/MeOH 10% H₂O/MeOH 10% H₂O/MeOH Amount (mL) 15 15 12 12 Acid/Cr 0.013 0.000 Alcohol/Cr 0.374 0.258 GC-MS/Cr 0.009 0.465 0.270 0.500 Total/Cr 0.383 0.723 0.270 0.500 Oxygenated ethanol 90% t-butanol 40% 2-pentanol 49% 2-pentanol 47% Products methanol  6% i-butanol 29% 2-pentanone 33% 2-pentanone 36% acetic acid  3% acetone 10% 1-pentanol 18% 1-pentanol 17% isopropanol  1% isopropanol  5% n-propanol  1% isobutanal  5% Example 17 18 19 20 Catalyst C D E D Weight (g) 1.9 2.0 2.6 2.0 Reductant n-Pentane n-Pentane n-Pentane n-Pentane Amount 0.5 mL 0.5 mL 2 mL 2 mL Light 3 hr Blue 7 hr Blue 26 hr UV 26 hr UV Color Black Blue-gray Blue-gray Blue-gray Hydrolysis 10% H₂O/MeOH Vitamin C 5% H₂O/MeOH 5% H₂O/MeOH Amount (mL) 11 30 10 10 Acid/Cr 0.000 0.000 0.000 0.042 Alcohol/Cr 0.000 0.000 GC-MS/Cr 0.207 1.140 0.143 0.499 Total/Cr 0.207 1.140 0.143 0.541 Oxygenated 2-pentanone 62% 2-pentanol 63% 2-pentanol 41% 2-pentanol 39% Products 2-pentanol 14% 1-pentanol 19% 1-pentanol 23% 1-pentanol 21% 3-pentanone 10% pentanal 18% 2-pentanone 21% 2-pentanone 15% 3-penten-2-one  3% 3-pentanone 11% 3-pentanone 10% 1-pentanol  2% C10H18O  4% formic acid  8% 3-penten-2-one  2% 2-pentenal  2% Example 21 22 23 24 Catalyst L D E D Weight (g) 3.0 1.9 2.3 1.1 Reductant n-Pentane i-Pentane i-Pentane i-Pentane Amount 2 mL 0.5 mL 0.5 mL 2 mL Light UV 24 h 7 hr Blue 31 hr Blue 4.5 hr UV Color Brown Blue-gray Blue-gray Gray-blue Hydrolysis 4% H₂O/MeOH 10% H₂O/MeOH H₂O + CH₃CN 5% H₂O/MeOH Amount (mL) 15 40 15 15 Acid/Cr 0.002 0.000 0.000 0.006 Alcohol/Cr 0.005 0.347 GC-MS/Cr 0.077 0.850 0.929 0.600 Total/Cr 0.083 0.850 0.929 0.953 Oxygenated 2-pentanol 40% t-pentanol 24% 2-pentanol 31% ethanol 27% Products 2-pentanone 21% 3-Me-2-butanol 23% acetic acid 23% 2-Me-1-butanol 18% 1-pentanol 15% Me-butanol 22% 2-pentanol 22% t-pentanol 17% 3-pentanone  9% isoamyl alcohol 13% 3-pentanol 11% 3-Me-2-butanol 10% isopropanol  4% 2-Me-butanal 11% C5H4O3  7% isoamyl alcohol  9% C10H18O  2% 3-Me-2-butanone  7% isobutanol  8% C7H14O  2% 3-Me-2-butanone  6% formic acid  2% C6H12O3  3% Example 25 26 27 28 Catalyst J F H1 G1 Weight (g) 2.2 2.4 1.9 1.9 Reductant i-Pentane i-Pentane i-Pentane i-Pentane Amount 0.5 mL 0.5 mL 0.5 mL 0.5 Light 31 hr Blue 31 hr Blue 40 hr Blue 40 hr Blue Color Dark red Blue-gray-black Green-brown Green-brown Hydrolysis H₂O + CH₃CN H₂O + CH₃CN H₂O + CH₃CN H₂O + CH₃CN Amount (mL) 15 15 15 15 Acid/Cr 0.004 0.004 0.004 0.016 Alcohol/Cr GC-MS/Cr 0.744 0.042 0.061 0.052 Total/Cr 0.747 0.046 0.064 0.068 Oxygenated 2-Me-2-butanol 41% 3-Me-1-butanol 26% C5H12O alcohol 25% C5H12O 23% Products 3-Me-2-butanol 21% 2-Me-1-butanol 24% C5H8O aldehyde 22% 2-Me-2-butenal 23% 2-Me-1-butanol 15% 2-Me-2-butenal 24% C5H12O 17% C5H12O2 13% 3-Me-2-butanone  9% 3-Me-2-butenal  5% 3-Me-2-pentanone  5% formic acid 12% 3-Me-1-butanol  9% acetic acid  4% C5H12O2  5% C5H12O 12% C10/C11  2% C5H10O2  4% C6H10O  4% acetic acid 11% dioxygenate formic acid  4% 4-OH-3-Me-2-  3% 2-pentenal  2% butanone formic acid  3% C5H10O  3% 3-Me-2 butenal  2% acetic acid  2% Example 29 30 31 32 Catalyst D B B B Weight (g) 2.1 2.1 1.2 1.5 Reductant Cyclopentane n-Hexane Cyclohexane Decalin Amount 0.5 mL 0.5 mL 0.5 g Light 7 hr Blue 3.3 hr UV 2 hr Blue LED 2 hr Blue LED Color Blue-gray Blue-gray Deep blue Light blue Hydrolysis 10% H₂O/MeOH 10% H₂O/MeOH 10% H₂O/MeOH 10% H₂O/MeOH Amount (mL) 40 12 12 12 Acid/Cr 0.000 No data No data Alcohol/Cr No data No data GC-MS/Cr 0.606 0.573 No data No data Total/Cr 0.606 0.573 Oxygenated cyclopentanol 85% 2-hexanol 25% cyclohexanol 49% decalols, 17% Products cyclopentanone 15% 2-hexanone 23% cyclohexanone 40% C10H18O 3-hexanol 20% 2-cyclohexen-1-  7% decalones, 16% 3-hexanone 17% one C10H18O 1-hexanol 15% cyclohexanediol  2% C10H14O  2% C14H22O  1% C10H14O2  1% C6H10O2  1% naphthalenone  1% Example 33 34 35 36 Catalyst B B K A Weight (g) 1.1 1.6 3.3 2.0 Reductant Adamantane Toluene Toluene Ethylene Amount 0.5 g 0.5 mL 2 mL 10 psig Light 2 hr Blue LED 1.5 hr Blue UV 24 h 9 hr Sun Color Blue Blue-black Brown Blue-gray Hydrolysis 10% H₂O/MeOH 10% H₂O/MeOH 4% H₂O/MeOH H₂O Amount (mL) 12 6 15 20 Acid/Cr No data 0.001 0.096 Alcohol/Cr No data 0.003 0.108 GC-MS/Cr No data 0.567 0.129 Total/Cr 0.567 0.133 0.204 Oxygenated adamantone 32% benzaldehyde 41% benzaldehyde 77% methanol 51% Products adamantol 25% benzyl alcohol 17% benzyl alcohol 20% formic acid 46% adamantan-2-ol 20% C14H12O  9% isopropanol  2% n-propanol  2% C10H14O 16% benzophenone  8% formic acid  1% acetic acid  1% adamantanediol  2% C14H12O  6% C11H20O  1% C14H12O  6% 4-Me phenol  5% 2-Me phenol  5% Example 37 38 39 40 Catalyst B D D D Weight (g) 2.1 2.4 2.1 2.1 Reductant Ethylene Ethylene Ethylene Ethylene Amount 10 psig 15 psig (−78 C.) 15 psig (−78 C.) 15 psig (−78 C.) Light 9 hr Sun 60 hr Blue 24 hr Blue 24 hr Blue Color Blue-gray Blue-green Blue-green Blue-green Hydrolysis 0.1N NaOH 0.1N NaOH 0.1N NaOH 0.1N NaOH Amount (mL) 20 15 15 15 Acid/Cr 0.233 0.110 0.136 0.144 Alcohol/Cr 0.101 0.162 0.111 0.401 GC-MS/Cr 0.035 0.071 0.162 Total/Cr 0.335 0.272 0.318 0.675 Oxygenated formic acid 68% formic acid 39% formic acid 48% ethanediol 72% Products methanol 28% methanol 29% ethanediol 25% formic acid 20% acetic acid  1% ethanediol 27% methanol 24% diethylene glycol  4%  1% ethanol  2% ethanol  2% methanol  2% acetic acid  1% n-propanol  1% acetic acid  1% n-propanol  1% propionic acid  1% ethanol  1% acetic acid  1% Example 41 42 43 44 Catalyst E D D D Weight (g) 2.3 2.0 1.5 2.1 Reductant Ethylene Ethylene 1-Pentene 1-Pentene Amount 15 psig 15 psig 0.5 mL 0.5 mL Light 24 hr UV 24 hr UV 14 hr Blue Dark-24 hr Color Blue-gray Hydrolysis H₂O + CH₃CN H₂O + CH₃CN H₂O H₂O Amount (mL) 15 15 20 15 Acid/Cr 0.461 0.181 0.245 0.012 Alcohol/Cr 0.136 0.069 0.044 GC-MS/Cr 0.017 0.190 1.047 0.016 Total/Cr 0.614 0.436 1.193 0.072 Oxygenated acetic acid 38% formic acid 35% C8H18O 17% 1-butanol 29% Products formic acid 36% ethanediol 32% formic acid 13% formic acid 14% methanol 19% methanol 12% C10 or C11 alcohol 12% n-propanol  9% ethanediol  2% diethylene glycol 11% 1,2-pentanediol  7% ethanediol  8% ethanol  2% acetic acid  6% C9H20O  7% 1,2-pentandiol  8% n-propanol  1% ethanol  3% C8-C10 alcohol  6% methanol  8% 2-heptanone  5% 2-pentenal  7% C7H14O3  4% acetone  5% C10H22O  4% 2-penten-1-ol  3% isoamyl alcohol  3% ethanol  2% acetic acid  3% 3-pentanol  2% Example 45 46 47 48 Catalyst D D D D Weight (g) 2.0 1.9 1.7 1.5 Reductant 1-Pentene 1-Pentene 1-Hexene 1-Hexene Amount 0.5 mL 0.5 mL 0.5 mL 0.5 mL Light 24 hr UV 2 hr UV 7 hr Blue 14 hr Blue Color Magenta Sky blue Blue-gray Blue-gray Hydrolysis H₂O H₂O 10% H₂O/MeOH H₂O Amount (mL) 15 15 40 20 Acid/Cr 0.015 0.018 0.036 0.248 Alcohol/Cr 0.000 0.091 GC-MS/Cr 0.087 0.124 1.315 Total/Cr 0.102 0.233 0.036 1.548 Oxygenated 1,2-pentanediol 31% 1-butanol 20% formic acid 100% hexanoic acid 41% Products 2-pentenal 13% 1,2-pentanediol 17% formic acid 10% formic acid 11% 2-pentenal 11% 2-hexanone  8% C10H22O 10% n-propanol  7% 2-octanone  3% C5H10O2  5% ethanediol  7% 1,2-hexanediol  3% 2-heptanone  5% formic acid  6% 1-hexen-3-ol  3% C8-11 oxygenate  3% ethyl ether  5% 3-penten-2-ol  3% C8-10 oxygenate  3% propanoic acid Me-nonanol  2% C9-11 oxygenate  3% 2-penten-1-ol  5% Me-heptanol  2% C5 di-oxygenate  2% ethanol  3% butyric acid  2% C10H20O  2% 2-heptanone  2% 2-hexanol  2% methanol  2% 2-hexenal  2% 2-Me-2-pentenal  2% Example 49 50 51 52 Catalyst D D D D Weight (g) 2.1 2.1 2.0 1.2 Reductant 1-Hexene 1-Hexene 1-Hexene 1-Hexene Amount 0.5 mL 0.5 mL 0.5 mL 2 mL Light 14 hr Blue 31 hr Blue 31 hr Blue 4.5 hr UV Color Blue-gray Blue-gray Blue-gray Blue-green Hydrolysis Vitamin C H₂O + CH₃CN 0.1N HCl + Fe⁺² 5% H₂O/MeOH Amount (mL) 20 15 15 15 Acid/Cr 0.058 0.082 0.038 0.007 Alcohol/Cr 0.198 GC-MS/Cr 0.426 0.153 0.095 0.458 Total/Cr 0.426 0.235 0.133 0.663 Oxygenated 1-hexene-3-ol 19% formic acid 35% formic acid 28% ethanol 22% Products hexanoic acid 14% 1-hexen-3-ol 18% 1-hexen-3-ol 24% 2-hexen-1-ol 15% 1,2-hexanediol 14% 1,2-hexanediol 12% 1,2-hexanediol 18% 1-hexen-3-ol 13% C6 oxygenate 10% C6H14O2-Si  8% C6H12O  9% 3-hexanone 11% formic acid  9% 2-hexenal  6% 2-hexenal  9% 2-hexenal 10% 2-hexen-1-ol  7% dimethylbutanol  4% 2-hexen-1-ol  7% 2-hexanol  9% C5/C6 oxygenate  6% 2-hexene-1-ol  4% 2-hexanol  5% n-propanol  7% acetic acid  5% 2-octanone  3% 2-hexanone  6% 2-hexnaone  2% 1,2-hexanediol  5% hexanal  2% C6H12O  2% 2-hexanol  2% Example 53 54 55 56 Catalyst E D D D Weight (g) 2.0 1.6 2.2 2.0 Reductant 1-Hexene 1-Hexene 1-Hexene 1-Hexene Amount 0.5 mL 0.5 mL 0.5 mL 0.5 mL Light 24 hr UV 2 hr UV Dark-24 hr 24 hr UV Color Blue-gray Magenta Hydrolysis H₂O + CH₃CN H₂O H₂O H₂O Amount (mL) 15 10 15 15 Acid/Cr 0.127 0.011 0.011 0.011 Alcohol/Cr 0.069 0.021 0.010 0.013 GC-MS/Cr 0.012 0.040 0.163 0.134 Total/Cr 0.208 0.072 0.184 0.159 Oxygenated acetic acid 58% 1.2-hexanediol 26% 1-hexen-3-ol 28% 1-hexen-3-ol 19% Products methanol 13% formic acid 15% 2-hexenal 17% 1,2-hexanediol 15% ethanol 10% ethanol 14% 1,2-hexanediol 13% 2-hexenal 12% 1-butanol  7% isobutanol 12% C6H12O  8% 2-hexanone  9% 1,2-hexanediol  6% C6H14O  7% C6H12O  7% 2-hexen-1-ol  6% formic acid  4% C9/C10 oxygenate  6% 2-hexen-1-ol  6% formic acid  6% n-propanol  3% 1-hexanol  3% formic acid  5% C6H12O  5% 1-butanol  3% dimethylbutanoic  5% C6H12O2  4% 1-pentanol  2% acid hexenal  4% 2-hexanone  2% 1-butanol  3% 1-butanol  4% 3-Me-2-pentanone  2% C6H14O  3% 2-hexanol  3% Example 57 58 59 60 Catalyst D J F H1 Weight (g) 2.0 2.6 2.8 1.9 Reductant 1-Hexene 1-Hexene 1-Hexene 1-Hexene Amount 0.5 mL 0.5 mL 0.5 mL 0.5 mL Light 2 hr UV 31 hr Blue 31 hr Blue 40 hr Blue Color Sky blue Dark red Blue-gray-black Green-brown Hydrolysis H₂O H₂O + CH₃CN H₂O + CH₃CN H₂O + CH₃CN Amount (mL) 15 15 15 15 Acid/Cr 0.012 0.010 0.001 0.003 Alcohol/Cr 0.014 GC-MS/Cr 0.102 0.496 0.794 0.155 Total/Cr 0.127 0.506 0.795 0.158 Oxygenated 1-hexen-3-ol 23% 1,2-hexanediol 37% 1,2-hexanediol 20% 3,4-hexanediol 9% Products 2-hexenal 15% 1-hexen-3-ol 14% 1-hexen-3-one 20% C6H10O ketone 9% 1,2-hexanediol 10% 5-hexen-2-ol 14% 2-hexenal 13% 2-hexanol 9% formic acid  8% 5-hexen-3-ol 11% butanoic acid 11% C6H12O alcohol 8% C6H12O  7% ethyl butanoate  5% ethyl ester 1-hexen-3-ol 8% C6H12O  7% 1-pentanol  4% 2-hexen-1-ol  7% 2,3-hexanediol 7% 2-hexen-1-ol  4% 2-hexen-1-ol  4% 2-hexanone  4% C6H12O alcohol 7% 1-butanol  4% 5-hexen-1-ol  4% 1-hexen-3-ol  3% C6H10O ketone 5% diMe butanoic acid  4% C6H12O  2% C6H12O alcohol  3% 2-hexanone 5% isobutanol  3% C6H12O  1% hexanediol  3% 2-hexenal 4% 2-hexen-1-ol  2% 2-hexenal  1% 2-hexen-1-ol  3% 1,2-hexanediol 2% 3-hexen-2-one  3% Example 61 62 63 64 Catalyst G1 K L D Weight (g) 2.1 2.9 2.7 1.9 Reductant 1-Hexene 1-Hexene 1-Hexene 2-Hexene Amount 0.5 mL 2 mL 2 mL 0.5 mL Light 40 hr Blue UV 24 h UV 24 h 14 hr Blue Color Green-brown Brown Brown Blue-gray Hydrolysis H₂O + CH₃CN 4% H₂O/MeOH 4% H₂O/MeOH H₂O Amount (mL) 15 15 15 20 Acid/Cr 0.012 0.003 0.003 0.145 Alcohol/Cr 0.003 0.004 GC-MS/Cr 0.147 0.025 0.051 2.318 Total/Cr 0.159 0.031 0.058 2.462 Oxygenated 1-hexen-3-ol 18% 5-hexen-2-ol 21% 5-hexen-2-ol 17% 2,3-hexanediol 21% Products C6H12O 10% 5-hexen-2-one 16% 5-hexene-ol 13% 3-hexen-2-one 17% 1.2-hexanediol  9% 5-hexen-3-ol 15% 1-hexen-3-ol 10% 4-hexen-3-one 11% C6H12O  8% 1-hexen-3-ol  7% 5-hexen-2-one  9% 3,4-hexanediol  8% 2-hexanol  8% isopropanol  7% 1-pentanol  6% 4-hexen-3-ol  8% C6H12O  7% formic acid  7% C11/12 oxygenate  4% 2-Me-1-penten-3-ol  8% C6H14O2  7% 1-pentanol  7% formic acid  4% 1-hexen-3-ol  5% 2.3-hexanediol  5% 5-hexene-ol  7% isopropanol  4% 2-hexenal  3% C6H12O  4% 4-hexen-3-one  4% 5-hexen-1-ol  3% formic acid  3% acetic acid  3% ethanol  3% C10-12 oxygenate  3% C6H12O  2% 2-hexen-1-ol  3% 2-hexenal  3% 1,2-hexandiol  3% 2-butenal  2% formic acid  3% pentanal  3% 4-hexen-1-ol  2% Example 65 66 67   Catalyst D D D Weight (g) 2.3 2.2 2.0 Reductant n-Pentane n-Pentane n-Pentane Amount 0.25 mL 1 mL 3 mL Light UV 24 hr UV 24 hr UV 24 hr Color Dark blue-gray Green Dark blue-gray Hydrolysis 5% H₂O/MeOH 5% H₂O/MeOH 5% H₂O/MeOH Amount (mL) 15 15 15 Acid/Cr 0.13 0.011 0.012 Alcohol/Cr GC-MS/Cr 0.323 1.819 1.074 Total/Cr 0.336 1.831 1.086 Oxygenated 2-pentanol 46% 2-pentanol 39% 2-pentanol 62% Products 1-pentanol 21% 1-pentanol 16% 2-pentanone 18% 2-pentanone 13% 2-pentanone 13% 3-pentanone  9% 3-pentanone  6% 3-pentanone  6% 1-pentanol  3% 2-hexenal  5% C5H10O  4% 2-pentenal  2% formic acid  3% C10H18O  2% 3-penten-2-one  2% 2-pentenal  2% C7H12O  2% C7H12O  2% 2-Me-2-butenal  2% C8H14O  1% formic acid  1%

Examples 68-74

Examples 68-74 were performed to determine the extent of reduction of the hexavalent chromium and the average valence after reduction in a representative supported chromium catalyst. Table II summarizes the results. Example 74 was a chromium/silica-titania catalyst containing approximately 0.8 wt. % chromium and 7 wt. % titania, and having a BET surface area of 530 m²/g, a pore volume of 2.6 mL/g, and an average particle size of 130 um, which was calcined in dry air at 850° C. for 3 hr to convert chromium to the hexavalent oxidation state (orange). This converted over 86 wt. % of the chromium into the hexavalent state. For Examples 68-69, approximate 2 g samples of the catalyst of Example 74 were separately charged to a glass reaction vessel and 0.5 mL of liquid isopentane was charged to the vessel. For Examples 70-71, about 1.5 atm of gaseous ethane was charged to the glass bottle. Then, the bottle was placed in a light-proof box under blue fluorescent light (approximately 2 times the intensity expected from sunlight), and the bottle was continuously rotated so that all of the catalyst was exposed to the light for 24 hr. The final catalyst color is noted in Table II. Afterward, into the bottle, along with the catalyst, was introduced about 20 mL of a solution of 2 M H₂SO₄. To this was added 5 drops of ferroin Fe(+3) indicator. This usually turned a blue-green color indicating the presence of Fe(III) ions. Next, the solution was titrated to the ferroin endpoint (red color) using a solution of ferrous ammonium sulfate, which had been previously calibrated by reaction with a standardized 0.1 M sodium dichromate solution. When the solution turned red, the end point was signaled, and the titrant volume was recorded, to calculate the oxidation capacity of the catalyst, expressed as wt. % Cr(VI) and as percent reduced, that is, the percent of the original Cr(VI) oxidative power that has been removed by the reduction treatment. The average valence was also computed by multiplying the percent reduced by +3 and subtracting that number from +6.

Of course, this treatment gives only an average oxidation state. Note that although Table II lists the oxidative power measured as wt. % Cr(VI), in reality all of the chromium could be present in lower valence states, such as Cr(IV) or Cr(V). Thus, the Cr(VI) value in Table II only lists the maximum amount of Cr(VI) that could be present. More likely, the reduced chromium catalysts have a combination of several valence states that produce the measured oxidative power. Note that some of the reduced chromium, and particularly those catalysts reduced with CO, may be in the divalent state, which would not have been detected in this test, which stops in the trivalent state.

Example 74 demonstrates that the air-calcined chromium catalyst contained substantially most of its chromium (0.69/0.80=86 wt. %) present as Cr(VI), and it is this Cr(VI) amount that is being reduced in the light treatment. Therefore, this amount of Cr(VI) serves as the starting amount, which had an average valence of +6, and which serves as a reference, to which the reduced catalysts are then compared. Examples 68-69 were reduced chromium catalysts with an average valence of approximately +3.3, with no more than 0.06 wt. % Cr(VI), and with less than 10 wt. % of the starting hexavalent chromium still remaining in the hexavalent oxidation state. Examples 70-71 were reduced chromium catalysts with an average valence of approximately +4.1, with no more than 0.26 wt. % Cr(VI), and with less than 40 wt. % of the chromium in the hexavalent oxidation state. For Examples 72-73, the supported chromium catalyst was reduced in CO with either blue light or elevated temperature, resulting in no oxidative power being measured (0 wt. % Cr(VI) in the table). Thus, the average valence must be no more than +3. But the supported chromium catalyst that was CO-reduced by conventional means (Example 73) is known to have a valence of mostly Cr(II) after reduction, which is not detected in this test. Accordingly, Examples 72 and 73 are listed as less than or equal to +3. Notably, this test cannot distinguish between Cr(II) and Cr(III) species, but there was no measurable amount of hexavalent chromium in Examples 72-73.

TABLE II Examples 68-74 Catalyst Cr (VI) Reduced Average Example Reductant Treatment Color (g) (wt. %) (wt. %) Valence 68 isopentane Blue light blue 2.05 0.06 90.8 3.28 24 hr 69 isopentane Blue light blue 2.08 0.06 90.9 3.27 24 hr 70 ethane Blue light olive 2.14 0.26 62.3 4.13 24 hr green 71 ethane Blue light olive 2.30 0.26 61.9 4.14 24 hr green 72 CO Blue light blue 2.33 0.00 100 ≤3 24 hr green 73 CO CO reduction blue 2.52 0.00 100 ≤3 30 min-350° C. 74 None None orange — 0.69 0 6.00

The invention is described above with reference to numerous aspects and specific examples. Many variations will suggest themselves to those skilled in the art in light of the above detailed description. All such obvious variations are within the full intended scope of the appended claims. Other aspects of the invention can include, but are not limited to, the following (aspects are described as “comprising” but, alternatively, can “consist essentially of” or “consist of”):

Aspect 1. A process for converting an olefin reactant into a diol compound, the process comprising:

(i) contacting the olefin reactant and a supported chromium catalyst comprising chromium in a hexavalent oxidation state to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst (e.g., with at least a portion of the chromium on the reduced chromium catalyst having at least one bonding site with a hydrocarboxy group (a —O-hydrocarbon group)); and

(ii) hydrolyzing the reduced chromium catalyst to form a reaction product comprising the diol compound.

Aspect 2. A process for converting an olefin reactant into a diol compound, the process comprising:

(i) irradiating the olefin reactant and a supported chromium catalyst comprising chromium in a hexavalent oxidation state with a light beam at a wavelength in the UV-visible spectrum to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst; and

(ii) hydrolyzing the reduced chromium catalyst to form a reaction product comprising the diol compound.

Aspect 3. The process defined in aspect 1 or 2, wherein the olefin reactant comprises a linear olefin compound (e.g., a normal α-olefin), a branched olefin compound, a cyclic olefin compound, or a combination thereof.

Aspect 4. The process defined in aspect 1 or 2, wherein the olefin reactant comprises any suitable carbon number olefin compound or any carbon number olefin compound disclosed herein, e.g., a C₂ to C₃₆ olefin compound, a C₂ to C₁₈ olefin compound, a C₂ to C₁₂ olefin compound, or a C₂ to C₈ olefin compound (e.g., a C₂-C₁₈ normal α-olefin or a C₂-C₈ normal α-olefin).

Aspect 5. The process defined in aspect 1 or 2, wherein the olefin reactant comprises ethylene, propylene, butene, pentene, hexene, heptene, octene, decene, dodecene, tetradecene, hexadecene, octadecene, or any combination thereof.

Aspect 6. The process defined in aspect 1 or 2, wherein the olefin reactant comprises ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-octadecene, styrene, or any combination thereof.

Aspect 7. The process defined in aspect 1 or 2, wherein the olefin reactant comprises ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, or any combination thereof.

Aspect 8. The process defined in aspect 1 or 2, wherein the olefin reactant comprises ethylene, propylene, 1-butene, 1-pentene, 1-hexene, or any combination thereof.

Aspect 9. The process defined in aspect 1 or 2, wherein the olefin reactant comprises norbornene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, or any combination thereof.

Aspect 10. The process defined in aspect 1 or 2, wherein the olefin reactant comprises ethylene (or propylene), and the diol compound comprises ethanediol (or propanediol).

Aspect 11. The process defined in aspect 1 or 2, wherein the olefin reactant comprises 1-pentene, and the diol compound comprises a pentanediol.

Aspect 12. The process defined in aspect 1 or 2, wherein the olefin reactant comprises 1-hexene, and the diol compound comprises a hexanediol.

Aspect 13. The process defined in any one of the preceding aspects, wherein the diol compound comprises a 1,2-diol compound.

Aspect 14. The process defined in any one of the preceding aspects, wherein the diol compound comprises a 1,3-diol compound.

Aspect 15. The process defined in any one of the preceding aspects, wherein the diol compound comprises a 2,3-diol compound.

Aspect 16. The process defined in any one of the preceding aspects, wherein the olefin reactant comprises a Cn olefin compound, and the diol compound comprises a Cn diol compound.

Aspect 17. The process defined in aspect 16, wherein n is any suitable integer or an integer in any range disclosed herein, e.g., from 2 to 36, from 2 to 18, from 2 to 12, or from 2 to 8.

Aspect 18. The process defined in any one of the preceding aspects, wherein the reaction product further comprises a carbonyl compound, e.g., an aldehyde, a ketone, a carboxylic acid, or any combination thereof.

Aspect 19. The process defined in any one of the preceding aspects, wherein the reaction product further comprises an alcohol compound (a mono-alcohol compound).

Aspect 20. The process defined in any one of the preceding aspects, wherein the supported chromium catalyst and the reduced chromium catalyst comprise any suitable amount of chromium or an amount in any range disclosed herein, e.g., from about 0.01 to about 50 wt. %, from about 0.01 to about 10 wt. %, from about 0.05 to about 15 wt. %, from about 0.1 to about 15 wt. %, from about 0.2 to about 10 wt. %, from about 0.1 to about 5 wt. %, from about 0.5 to about 30 wt. %, or from about 0.5 to about 2.5 wt. % of chromium, based on the weight of the supported chromium catalyst or the reduced chromium catalyst.

Aspect 21. The process defined in any one of the preceding aspects, wherein the reduced chromium catalyst comprises any suitable amount of chromium in an average oxidation state of +5 or less, or an amount in any range disclosed herein, e.g., from about 0.01 to about 50 wt. %, from about 0.01 to about 10 wt. %, from about 0.05 to about 15 wt. %, from about 0.1 to about 15 wt. %, from about 0.2 to about 10 wt. %, from about 0.1 to about 5 wt. %, from about 0.5 to about 30 wt. %, or from about 0.5 to about 2.5 wt. % of chromium in an average oxidation state of +5 or less, based on the weight of the reduced chromium catalyst.

Aspect 22. The process defined in any one of the preceding aspects, wherein the amount of the chromium of the supported chromium catalyst in a hexavalent oxidation state is at least about 10 wt. %, at least about 20 wt. %, at least about 40 wt. %, at least about 60 wt. %, at least about 80 wt. %, or at least about 90 wt. %, based on the total amount of chromium on the supported chromium catalyst, and/or the amount of chromium of the reduced chromium catalyst in a hexavalent oxidation state is (from 0 wt. %, from about 0.5 wt. %, from about 1 wt. %, or from about 2 wt. % to) less than or equal to about 50 wt. %, less than or equal to about 40 wt. %, less than or equal to about 30 wt. %, or less than or equal to about 15 wt. %, based on the total amount of chromium on the reduced chromium catalyst.

Aspect 23. The process defined in any one of the preceding aspects, wherein at least about 10 wt. %, at least about 20 wt. %, at least about 40 wt. %, at least about 60 wt. %, at least about 80 wt. %, or at least about 90 wt. %, of the supported chromium catalyst is reduced to form the reduced chromium catalyst, based on the total amount of the supported chromium catalyst.

Aspect 24. The process defined in any one of the preceding aspects, wherein the chromium in the reduced chromium catalyst has an average valence of less than or equal to about 5.25, less than or equal to about 5, less than or equal to about 4.75, less than or equal to about 4.5, less than or equal to about 4.25, or less than or equal to about 4.

Aspect 25. The process defined in any one of aspects 1-24, wherein the supported chromium catalyst and the reduced chromium catalyst comprise any suitable solid oxide or any solid oxide disclosed herein, e.g., silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, silica-titania, silica-zirconia, alumina-titania, alumina-zirconia, zinc-aluminate, alumina-boria, alumina borate, silica-boria, aluminophosphate-silica, titania-zirconia, or any combination thereof.

Aspect 26. The process defined in any one of aspects 1-24, wherein the supported chromium catalyst and the reduced chromium catalyst comprise silica, silica-alumina, silica-coated alumina, silica-titania, silica-titania-magnesia, silica-zirconia, silica-magnesia, silica-boria, aluminophosphate-silica, alumina, alumina borate, or any combination thereof.

Aspect 27. The process defined in any one of aspects 1-24, wherein the supported chromium catalyst and the reduced chromium catalyst comprise a chemically-treated solid oxide comprising a solid oxide (e.g., as in aspect 25 or 26, such as silica, alumina, silica-alumina, silica-titania, silica-zirconia, silica-yttria, aluminophosphate, zirconia, titania, thoria, or stania) treated with an electron-withdrawing anion.

Aspect 28. The process defined in aspect 27, wherein the electron-withdrawing anion comprises sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, phospho-tungstate, tungstate, molybdate, or any combination thereof.

Aspect 29. The process defined in aspect 27 or 28, wherein the chemically-treated solid oxide contains from about 1 to about 30 wt. %, from about 2 to about 20 wt. %, from about 2 to about 15 wt. %, from about 3 to about 12 wt. %, or from 4 to 10 wt. %, of the electron-withdrawing anion, based on the total weight of the chemically-treated solid oxide.

Aspect 30. The process defined in any one of aspects 1-24, wherein the supported chromium catalyst and the reduced chromium catalyst comprise a chemically-treated solid oxide comprising fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, fluorided-chlorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or any combination thereof.

Aspect 31. The process defined in any one of aspects 1-24, wherein the supported chromium catalyst and the reduced chromium catalyst comprise chromium/silica, chromium/silica-titania, chromium/silica-titania-magnesia, chromium/silica-alumina, chromium/silica-coated alumina, chromium/aluminophosphate, chromium/alumina, chromium/alumina borate, or any combination thereof.

Aspect 32. The process defined in any one of aspects 1-24, wherein the supported chromium catalyst and the reduced chromium catalyst comprise chromium/silica-titania, and the supported chromium catalyst and the reduced chromium catalysts comprise any suitable amount of titanium or an amount in any range disclosed herein, e.g., from about 0.1 to about 20 wt. %, from about 0.5 to about 15 wt. %, from about 1 to about 10 wt. %, or from about 1 to about 6 wt. %, based on the weight of the supported chromium catalyst or the reduced chromium catalyst.

Aspect 33. The process defined in any one of aspects 1-24, wherein the supported chromium catalyst and the reduced chromium catalyst comprise chromium/sulfated alumina, chromium/fluorided alumina, chromium/fluorided silica-alumina, chromium/fluorided silica-coated alumina, or any combination thereof.

Aspect 34. The process defined in any one of aspects 1-24, wherein the supported chromium catalyst and the reduced chromium catalyst comprise a zeolite.

Aspect 35. The process defined in aspect 34, wherein the supported chromium catalyst and the reduced chromium catalyst comprise a medium pore zeolite, a large pore zeolite, or a combination thereof.

Aspect 36. The process defined in aspect 34, wherein the zeolite comprises a ZSM-5 zeolite, a ZSM-11 zeolite, an EU-1 zeolite, a ZSM-23 zeolite, a ZSM-57 zeolite, an ALPO4-11 zeolite, an ALPO4-41 zeolite, a Ferrierite framework type zeolite, or a combination thereof.

Aspect 37. The process defined in aspect 34, wherein the supported chromium catalyst and the reduced chromium catalyst comprise an L-zeolite, a Y-zeolite, a mordenite, an omega zeolite, and/or a beta zeolite.

Aspect 38. The process defined in any one of aspects 34-37, wherein the supported chromium catalyst and the reduced chromium catalyst comprise the zeolite and any suitable amount of binder or an amount in any range disclosed herein, e.g., from about 3 wt. % to about 35 wt. %, or from about 5 wt. % to about 30 wt. % binder, based on the weight of the supported chromium catalyst and/or the reduced chromium catalyst.

Aspect 39. The process defined in any one of the preceding aspects, wherein the supported chromium catalyst and the reduced chromium catalyst have any suitable pore volume (total) or a pore volume (total) in any range disclosed herein, e.g., from about 0.1 to about 5 mL/g, from about 0.15 to about 5 mL/g, from about 0.1 to about 3 mL/g, or from about 0.15 to about 2 mL/g.

Aspect 40. The process defined in any one of the preceding aspects, wherein the supported chromium catalyst and the reduced chromium catalyst have any suitable BET surface area or a BET surface area in any range disclosed herein, e.g., from about 50 to about 2000 m²/g, from about 50 to about 700 m²/g, from about 50 to about 400 m²/g, from about 100 to about 1200 m²/g, from about 150 to about 525 m²/g, or from about 300 to about 1000 m²/g.

Aspect 41. The process defined in any one of the preceding aspects, wherein the supported chromium catalyst and the reduced chromium catalyst are in any suitable shape or form or any shape or form disclosed herein, e.g., powder, round or spherical (e.g., spheres), ellipsoidal, pellet, bead, cylinder, granule (e.g., regular and/or irregular), trilobe, quadralobe, ring, wagonwheel, monolith, or any combination thereof.

Aspect 42. The process defined in any one aspects 1-41, wherein the supported chromium catalyst and the reduced chromium catalyst have any suitable average (d0) particle size or an average (d0) particle size in any range disclosed herein, e.g., from about 10 to about 500 microns, from about 25 to about 250 microns, or from about 20 to about 100 microns.

Aspect 43. The process defined in any one aspects 1-41, wherein the supported chromium catalyst and the reduced chromium catalyst comprise pellets or beads having any suitable average size or an average size in any range disclosed herein, e.g., from about 1/16 inch to about ½ inch, or from about ⅛ inch to about ¼ inch.

Aspect 44. The process defined in any one of aspects 2-43, wherein the wavelength comprises a single wavelength or a range of wavelengths in the visible spectrum (from 380 nm to 780 nm).

Aspect 45. The process defined in any one of aspects 2-43, wherein the wavelength comprises a single wavelength or a range of wavelengths in the 200 nm to 750 nm range.

Aspect 46. The process defined in any one of aspects 2-43, wherein the wavelength comprises a single wavelength or a range of wavelengths in the 300 to 750 nm range, the 350 nm to 650 nm range, the 300 nm to 500 nm range, or the 300 nm to 400 nm range.

Aspect 47. The process defined in any one of aspects 2-43, wherein the wavelength comprises a single wavelength or a range of wavelengths below 600 nm, below 525 nm, or below 500 nm.

Aspect 48. The process defined in any one of aspects 2-47, wherein the wavelength is a single wavelength.

Aspect 49. The process defined in any one of aspects 2-47, wherein the wavelength is a range of wavelengths spanning at least 25 nm, at least 50 nm, at least 100 nm, or at least 200 nm.

Aspect 50. The process defined in any one of aspects 2-49, wherein the light beam has any suitable intensity or an intensity in any range disclosed herein, e.g., at least about 500 lumens, at least about 1000 lumens, at least about 2000 lumens, at least about 5000 lumens, at least about 10,000 lumens, or at least about 20,000 lumens.

Aspect 51. The process defined in any one of aspects 2-50, wherein the light beam has any suitable power or any power disclosed herein, e.g., at least about 50 watts, at least about 100 watts, at least about 200 watts, at least about 500 watts, at least about 1,000 watts, or at least about 2,000 watts.

Aspect 52. The process defined in any one of aspects 2-51, wherein the supported chromium catalyst is irradiated with any suitable illuminance or any illuminance disclosed herein, e.g., at least about 100 lux, at least about 500 lux, at least about 1000 lux, at least about 2000 lux, at least about 5000 lux, at least about 10,000 lux, at least about 20,000 lux, or at least about 100,000 lux.

Aspect 53. The process defined in any one of the preceding aspects, wherein the contacting step (or the irradiating step) is conducted at any suitable temperature or any temperature disclosed herein, e.g., less than about 200° C., less than about 100° C., less than about 40° C., from about −100° C. to about 100° C., from about 0° C. to about 100° C., or from about 10° C. to about 40° C.

Aspect 54. The process defined in any one of the preceding aspects, wherein the contacting step (or the irradiating step) is conducted for any suitable contacting (or exposure) time or for any contacting (or exposure) time disclosed herein, e.g., from about 15 sec to about 48 hr, from about 1 min to about 6 hr, from about 1 min to about 15 min, or from about 1 hr to about 8 hr.

Aspect 55. The process defined in any one of the preceding aspects, wherein the molar ratio of the olefin reactant to chromium (of the supported chromium catalyst) is in any suitable range or any range disclosed herein, e.g., at least about 0.25:1, at least about 0.5:1, at least about 1:1, at least about 10:1, at least about 100:1, at least about 1000:1, or at least about 10,000:1.

Aspect 56. The process defined in any one of aspects 1-55, wherein the olefin reactant is in a gas phase during the contacting step (or the irradiating step).

Aspect 57. The process defined in any one of aspects 1-55, wherein the olefin reactant is in a liquid phase during the contacting step (or the irradiating step).

Aspect 58. The process defined in any one of aspects 1-55, wherein the process comprises contacting (or irradiating) a slurry of the supported chromium catalyst in the olefin reactant.

Aspect 59. The process defined in any one of aspects 1-55, wherein the process comprises contacting the olefin reactant with a fluidized bed of the supported chromium catalyst (or irradiating while contacting or fluidizing the supported chromium catalyst).

Aspect 60. The process defined in any one of aspects 1-55, wherein the process comprises contacting the olefin reactant (e.g., in a gas phase or in a liquid phase) with a fixed bed of the supported chromium catalyst (or irradiating while contacting).

Aspect 61. The process defined in any one of the preceding aspects, wherein the step of contacting (or irradiating) the olefin reactant with the supported chromium catalyst is conducted at any suitable WHSV or a WHSV in any range disclosed herein, e.g., from about 0.01 hr⁻¹ to about 500 hr⁻¹, or from about 0.1 hr⁻¹ to about 10 hr⁻¹.

Aspect 62. The process defined in any one of the preceding aspects, wherein the hydrolyzing step is conducted at any suitable temperature or any temperature disclosed herein, e.g., less than about 200° C., less than about 100° C., less than about 40° C., from about 0° C. to about 100° C., or from about 10° C. to about 40° C.

Aspect 63. The process defined in any one of the preceding aspects, wherein the hydrolyzing step comprises contacting the reduced chromium catalyst with a hydrolysis agent.

Aspect 64. The process defined in aspect 63, wherein the hydrolysis agent comprises any suitable hydrolysis agent or any hydrolysis agent disclosed herein, e.g., water, steam, an alcohol agent, an acid agent, an alkaline agent, or any combination thereof.

Aspect 65. The process defined in aspect 63 or 64, wherein the hydrolysis agent further comprises any suitable reducing agent or any reducing agent disclosed herein, e.g., ascorbic acid, an iron (II) reducing agent, a zinc reducing agent, or any combination thereof.

Aspect 66. The process defined in any one of the preceding aspects, wherein a conversion of the olefin reactant (or a yield to the diol compound) is any percent conversion (or yield) disclosed herein, e.g., at least about 2 wt. %, at least about 5 wt. %, at least about 10 wt. %, or at least about 15 wt. % (and up to about 99 wt. %, about 95 wt. about 90 wt. %, about 80 wt. %, about 70 wt. %, or about 50 wt. %).

Aspect 67. The process defined in any one of the preceding aspects, wherein a single pass conversion of the olefin reactant (or a single pass yield to the diol compound) is any single pass percent conversion (or single pass yield) disclosed herein, e.g., at least about 2 wt. %, at least about 5 wt. %, at least about 10 wt. %, or at least about 15 wt. % (and up to about 99 wt. %, about 95 wt. %, about 90 wt. %, about 80 wt. %, about 70 wt. %, or about 50 wt. %).

Aspect 68. The process defined in any one of the preceding aspects, wherein the yield to the diol compound per mole of chromium (VI) in the supported chromium catalyst is any molar ratio based on moles of chromium (VI) disclosed herein, e.g., at least about 0.01, at least about 0.05, at least about 0.1, or at least about 0.25 moles (and up to 2, up to about 1.8, up to about 1.6, up to about 1.4, up to about 1.2, or up to about 1 mole) of the diol compound.

Aspect 69. The process defined in any one of the preceding aspects, further comprising a step of separating at least a portion (and in some cases, all) of the olefin reactant from the reaction product after step (ii) to produce a separated portion of the olefin reactant using any suitable technique or any technique disclosed herein, e.g., extraction, filtration, evaporation, distillation, or any combination thereof.

Aspect 70. The process defined in aspect 69, wherein the separated portion of the olefin reactant is recycled and contacted (or irradiated) with the supported chromium catalyst again.

Aspect 71. The process defined in any one of the preceding aspects, further comprising a step of separating at least a portion (and in some cases, all) of the diol compound from the reaction product using any suitable technique or any technique disclosed herein, e.g., extraction, filtration, evaporation, distillation, or any combination thereof.

Aspect 72. The process defined in any one of the preceding aspects, further comprising a step of separating at least a portion (and in some cases, all) of the reduced chromium catalyst from the reaction product after step (ii) to produce a separated portion of the reduced chromium catalyst using any suitable technique or any technique disclosed herein, e.g., extraction, filtration, evaporation, distillation, or any combination thereof.

Aspect 73. The process defined in any one of the preceding aspects, further comprising a step of (iii) calcining the reduced chromium catalyst or the separated portion of the reduced chromium catalyst to regenerate the supported chromium catalyst.

Aspect 74. The process defined in aspect 73, wherein calcining comprises subjecting the reduced chromium catalyst or the separated portion of the reduced chromium catalyst to an oxidizing atmosphere at any suitable peak temperature and time conditions or any peak temperature and time conditions disclosed herein, e.g., a peak temperature from about 300° C. to about 1000° C., from about 500° C. to about 900° C., or from about 550° C. to about 870° C., for a time period of from about 1 min to about 24 hr, from about 1 hr to about 12 hr, or from about 30 min to about 8 hr. 

We claim:
 1. A process for converting an olefin reactant into a diol compound, the process comprising: (i) irradiating the olefin reactant and a supported chromium catalyst comprising chromium in a hexavalent oxidation state with a light beam at a wavelength in the UV-visible spectrum to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst; and (ii) hydrolyzing the reduced chromium catalyst to form a reaction product comprising the diol compound.
 2. The process of claim 1, wherein the olefin reactant comprises a C₂ to C₃₆ linear, branched, or cyclic olefin compound.
 3. The process of claim 1, wherein the olefin reactant comprises ethylene, propylene, butene, pentene, hexene, heptene, octene, decene, dodecene, tetradecene, hexadecene, octadecene, or any combination thereof.
 4. The process of claim 1, wherein the supported chromium catalyst contains from about 0.01 to about 50 wt. % of chromium, based on the weight of the supported chromium catalyst.
 5. The process of claim 1, wherein the reduced chromium catalyst contains chromium having an average valence of less than or equal to about 5.25.
 6. The process of claim 1, wherein the supported chromium catalyst comprises a solid oxide, a chemically-treated solid oxide, a zeolite, or a combination thereof.
 7. The process of claim 1, wherein the wavelength comprises a single wavelength or a range of wavelengths in a range from about 200 nm to about 750 nm.
 8. The process of claim 1, wherein the irradiating step is conducted at a temperature from about −100° C. to about 100° C.
 9. The process of claim 1, wherein the process comprises: contacting the olefin reactant with a fluidized bed of the supported chromium catalyst, and irradiating while contacting; or contacting the olefin reactant with a fixed bed of the supported chromium catalyst, and irradiating while contacting.
 10. The process of claim 1, wherein: hydrolyzing is conducted at a temperature from about 0° C. to about 100° C.; and hydrolyzing comprises contacting the reduced chromium catalyst with a hydrolysis agent comprising water, steam, an alcohol agent, an acid agent, an alkaline agent, or any combination thereof.
 11. The process of claim 1, wherein a conversion of the olefin reactant is at least about 10 wt. %.
 12. The process of claim 1, wherein a molar yield of the diol compound is from about 0.01 to about 2 moles of the diol compound per mole of chromium (VI) in the supported chromium catalyst.
 13. The process of claim 1, further comprising a step of separating at least a portion of the diol compound from the reaction product after step (ii).
 14. The process of claim 1, further comprising a step of separating at least a portion of the olefin reactant from the reaction product after step (ii), and wherein the at least a portion of the olefin reactant is recycled and irradiated with the supported chromium catalyst again.
 15. The process of claim 1, further comprising: separating at least a portion of the reduced chromium catalyst from the reaction product after step (ii); and calcining the at least a portion of the reduced chromium catalyst to regenerate the supported chromium catalyst.
 16. The process of claim 1, wherein: the olefin reactant comprises ethylene and the diol compound comprises ethanediol; the olefin reactant comprises propylene and the diol compound comprises propanediol; the olefin reactant comprises 1-pentene and the diol compound comprises a pentanediol; or the olefin reactant comprises 1-hexene and the diol compound comprises a hexanediol.
 17. A process for converting an olefin reactant into a diol compound, the process comprising: (i) contacting the olefin reactant and a supported chromium catalyst comprising chromium in a hexavalent oxidation state to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst; and (ii) hydrolyzing the reduced chromium catalyst to form a reaction product comprising the diol compound.
 18. The process of claim 17, wherein the olefin reactant comprises ethylene, propylene, 1-butene, 1-pentene, 1-hexene, or any combination thereof.
 19. The process of claim 17, wherein: the supported chromium catalyst contains from about 0.01 to about 50 wt. % of chromium, based on the weight of the supported chromium catalyst; and the reduced chromium catalyst contains chromium having an average valence of less than or equal to about 5.25.
 20. The process of claim 17, wherein the process comprises: contacting the olefin reactant with a fluidized bed of the supported chromium catalyst; or contacting the olefin reactant with a fixed bed of the supported chromium catalyst. 